U.S. patent number 7,951,518 [Application Number 10/581,974] was granted by the patent office on 2011-05-31 for polyester resin for toner, toner composition and resin particle.
This patent grant is currently assigned to Sanyo Chemical Industries, Ltd. Invention is credited to Takashi Akutagawa, Masakazu Iwata, Tsuyosi Izumi, Yasuhiro Ono, Tadao Takikawa, Shuhei Yahiro.
United States Patent |
7,951,518 |
Ono , et al. |
May 31, 2011 |
Polyester resin for toner, toner composition and resin particle
Abstract
Disclosed is a heat-fusible electrostatic image developing toner
which has an excellent balance between fixability at low
temperatures and grindability and is excellent in glossiness after
fixing. Also disclosed is a resin for toners. A polyester resin for
toners which is obtained by polycondensing a polyol component and a
polycarboxylic acid component is characterized by containing 20-100
weight % of one or more polyester resins (A1) having a storage
elastic modulus from 2.5.times.10.sup.3 Pa to 5.times.10.sup.6 Pa
at 150.degree. C. wherein the molar average cohesive energy of the
polyol component is between 7.0.times.10.sup.4 and
1.4.times.10.sup.5 J.
Inventors: |
Ono; Yasuhiro (Kyoto,
JP), Iwata; Masakazu (Kyoto, JP),
Akutagawa; Takashi (Kyoto, JP), Izumi; Tsuyosi
(Kyoto, JP), Takikawa; Tadao (Kyoto, JP),
Yahiro; Shuhei (Kyoto, JP) |
Assignee: |
Sanyo Chemical Industries, Ltd
(Kyoto, JP)
|
Family
ID: |
34682431 |
Appl.
No.: |
10/581,974 |
Filed: |
December 10, 2004 |
PCT
Filed: |
December 10, 2004 |
PCT No.: |
PCT/JP2004/018508 |
371(c)(1),(2),(4) Date: |
April 23, 2007 |
PCT
Pub. No.: |
WO2005/057293 |
PCT
Pub. Date: |
June 23, 2005 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20070281235 A1 |
Dec 6, 2007 |
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Foreign Application Priority Data
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Dec 10, 2003 [JP] |
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2003-412519 |
Feb 25, 2004 [JP] |
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2004-050305 |
May 19, 2004 [JP] |
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2004-149723 |
May 31, 2004 [JP] |
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2004-162599 |
Jun 30, 2004 [JP] |
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2004-192449 |
Jun 30, 2004 [JP] |
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2004-192592 |
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Current U.S.
Class: |
430/109.4;
524/601; 524/599; 430/111.4; 528/272 |
Current CPC
Class: |
G03G
9/08797 (20130101); C09D 5/03 (20130101); C08G
63/20 (20130101); G03G 9/081 (20130101); G03G
9/08755 (20130101); G03G 9/08795 (20130101) |
Current International
Class: |
G03G
9/00 (20060101) |
Field of
Search: |
;430/109.4,111.4
;524/599,601 ;528/272 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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03-050561 |
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Mar 1991 |
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JP |
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05-224461 |
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Sep 1993 |
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JP |
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06-003857 |
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Jan 1994 |
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JP |
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06-019197 |
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Jan 1994 |
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JP |
|
07-013385 |
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Jan 1995 |
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JP |
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08-101530 |
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Apr 1996 |
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JP |
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08-194336 |
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Jul 1996 |
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JP |
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10-078679 |
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Mar 1998 |
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JP |
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10-254170 |
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Sep 1998 |
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JP |
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10-260547 |
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Sep 1998 |
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JP |
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11-302361 |
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Nov 1999 |
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JP |
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11-305485 |
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Nov 1999 |
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JP |
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2003-005444 |
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Jan 2003 |
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JP |
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2003-107798 |
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Apr 2003 |
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JP |
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2003-176339 |
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Jun 2003 |
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JP |
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2003-201342 |
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Jul 2003 |
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JP |
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2003-207940 |
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Jul 2003 |
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JP |
|
2003-231744 |
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Aug 2003 |
|
JP |
|
2003-246920 |
|
Sep 2003 |
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JP |
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2003-262978 |
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Sep 2003 |
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JP |
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2003-302788 |
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Oct 2003 |
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JP |
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Other References
Japanese Office Action and Summary thereof (in English language)
describing the relevant parts of the Japanese Office Action. cited
by other.
|
Primary Examiner: Chapman; Mark A
Attorney, Agent or Firm: Edwards Angell Palmer & Dodge
LLP Umemuro; Jun Swiszcz; Lisa
Claims
The invention claimed is:
1. A polyester resin for a toner obtained by polycondensing a
polyol component and a polycarboxylic acid component, wherein the
polyol component has a molar average cohesive energy of
7.0.times.10.sup.4 to 1.4.times.10.sup.5 J and the polyester resin
contains 20 to 100% by weight of at least one kind of polyester
resin (A1) having a storage modulus in a range of
2.5.times.10.sup.3 Pa to 5.times.10.sup.6 Pa at 150.degree. C.
2. The polyester resin for a toner according to claim 1, wherein
the polyester resin (A1) has a softening point in a range from
120.degree. C. to 180.degree. C. and a loss tangent of 0.9 or
higher at a temperature in a range from 130.degree. C. to
200.degree. C.
3. The polyester resin for a toner according to claim 2, wherein
the polyester resin (A1) comprises the polyol component containing
30 to 100% by mole of an aliphatic diol having 2 to 6 carbon atoms
(at least a part of the aliphatic diol is 1,2-propylene glycol) and
has a number average molecular weight of 1000 to 9500 of
tetrahydrofuran-soluble fractions.
4. The polyester resin for a toner according to claim 2, wherein
the resin (A1) comprises a linear polyester resin and a non-linear
polyester resin.
5. The polyester resin for a toner according to claim 2, wherein
the resin (A1) is obtained by polycondensation in the presence of a
polymerization catalyst containing one or more metals selected from
the group consisting of titanium, antimony, zirconium, nickel, and
aluminum.
6. A polyester resin composition for a toner containing the
polyester resin for a toner according to claim 2 and an additive
(B) for a toner comprising a modified wax (w1) produced by
modifying at least a part of a wax (w) with a vinyl monomer
(m).
7. A toner composition containing the polyester resin for a toner
according to claim 2, a colorant, and if necessary, one or more
kinds of additives selected from the group consisting of a release
agent, a charge control agent, and a fluidizing agent.
8. The toner composition according to claim 7, wherein the toner
has 95.degree. C. or higher difference between the hot offset
occurrence temperature and the minimum fixing temperature in the
case of fixing of an un-fixed image by the toner using a fixing
apparatus.
9. A non-magnetic single component toner to be used in an image
formation method of developing a latent image by supplying a toner
to a latent image carrier, wherein the toner comprises the
polyester resin for a toner (A1) according to claim 2, a colorant,
and has physical properties within an area surrounded by straight
lines defined by the following equations (1) to (4) in
xy-coordinates of glass transition temperature (Tg) of (A1) as a
variant in x-axis and softening point (sp) in y-axis, and one or
more kinds of fine particle additives on the surface of the toner
particles, sp=4Tg-110, equation (1): sp=4Tg-170, equation (2):
sp=90, and equation (3): sp=130. equation (4):
10. The polyester resin for a toner according to claim 1, wherein
the polyester resin (A1) is obtained by polycondensing the
polycarboxylic acid component comprising 80 to 100% by mole of
terephthalic acid, isophthalic acid, and/or a lower alkyl (carbon
atoms of the alkyl: 1 to 4) ester of them (a) and the polyol
component comprising 20 to 100% by mole of an aliphatic diol (80 to
100% by mole of the aliphatic diol is 1,2-propylene glycol) (b);
and 0.1 to 20% by mole of the total of the polyol component and the
polycarboxylic acid component being tri- or higher polyhydric
alcohol and/or tri- or higher polycarboxylic acid (c), and has a
softening point in a range from 95 to 160.degree. C. and a glass
transition temperature (Tg) in a range from 45 to 75.degree. C.
11. The polyester resin for a toner according to claim 10, wherein
the resin (A1) comprises a linear polyester resin and a non-linear
polyester resin.
12. The polyester resin for a toner according to claim 10, wherein
the resin (A1) is obtained by polycondensation in the presence of a
polymerization catalyst containing one or more metals selected from
the group consisting of titanium, antimony, zirconium, nickel, and
aluminum.
13. A polyester resin composition for a loner containing the
polyester resin for a toner according to claim 10 and an additive
(B) for a toner comprising a modified wax (w1) produced by
modifying at least a part of a wax (w) with a vinyl monomer
(m).
14. A toner composition containing the polyester resin for a toner
according to claim 10, a colorant, and if necessary, one or more
kinds of additives selected from the group consisting of a release
agent, a charge control agent, and a fluidizing agent.
15. The toner composition according to claim 14, wherein the toner
has 95.degree. C. or higher difference between the hot offset
occurrence temperature and the minimum fixing temperature in the
case of fixing of an un-fixed image by the toner using a fixing
apparatus.
16. A non-magnetic single component toner to be used in an image
formation method of developing a latent image by supplying a toner
to a latent image carrier, wherein the toner comprises the
polyester resin for a toner (A1) according to claim 10, a colorant,
and has physical properties within an area surrounded by straight
lines defined by the following equations (1) to (4) in
xy-coordinates of glass transition temperature (Tg) of (A1) as a
variant in x-axis and softening point (sp) in y-axis, and one or
more kinds of fine particle additives on the surface of the toner
particles, sp=4Tg-110, equation (1): sp=4Tg-170, equation (2):
sp=90, and equation (3): sp=130. equation (4):
17. The polyester resin for a toner according to claim 1, wherein
the polyester resin (A1) comprises the polyol component containing
30 to 100% by mole of an aliphatic diol having 2 to 6 carbon atoms
(at least a part of the aliphatic diol is 1,2-propylene glycol) and
has a number average molecular weight of 1000 to 9500 of
tetrahydrofuran-soluble fractions.
18. The polyester resin for a toner according to claim 1, wherein
the resin (A1) comprises a linear polyester resin and a non-linear
polyester resin.
19. The polyester resin for a toner according to claim 1, wherein
the resin (A1) is obtained by polycondensation in the presence of a
polymerization catalyst containing one or more metals selected from
the group consisting of titanium, antimony, zirconium, nickel, and
aluminum.
20. A polyester resin composition for a toner containing the
polyester resin for a toner according to claim 1 and an additive
(B) for a toner comprising a modified wax (w1) produced by
modifying at least a part of a wax (w) with a vinyl monomer
(m).
21. A toner composition containing the polyester resin for a toner
according to claim 1, a colorant, and if necessary, one or more
kinds of additives selected from the group consisting of a release
agent, a charge control agent, and a fluidizing agent.
22. The toner composition according to claim 21, wherein the toner
has 95.degree. C. or higher difference between the hot offset
occurrence temperature and the minimum fixing temperature in the
case of fixing of an un-fixed image by the toner using a fixing
apparatus.
23. A non-magnetic single component toner to be used in an image
formation method of developing a latent image by supplying a toner
to a latent image carrier, wherein the toner comprises the
polyester resin for a toner (A1) according to claim 1, a colorant,
and has physical properties within an area surrounded by straight
lines defined by the following equations (1) to (4) in
xy-coordinates of glass transition temperature (Tg) of (A1) as a
variant in x-axis and softening point (sp) in y-axis, and one or
more kinds of fine particle additives on the surface of the toner
particles, sp=4Tg-110, equation (1): sp=4Tg-170, equation (2):
sp=90, and equation (3): sp=130. equation (4):
Description
TECHNICAL FIELD
The invention relates to a resin for a toner and a toner
composition to be used for electrophotography, electrostatic
recording, and electrostatic printing.
Moreover, the invention relates to resin particles. More
particularly, the invention relates to resin particles useful for
various uses such as a resin for slush molding, a powder coating,
an electrophotographic toner, an electrostatic recording toner, an
electrostatic printing toner, or hot-melt adhesive.
BACKGROUND ART
A toner for developing an electrostatic image to be used for a heat
fixing method is required to be not fuse with a heat roll even at a
high fixing temperature (hot offset resistance); fixed even at a
low fixing temperature (low temperature fixing property); and good
in the grindability of a resin thereof used in producing the toner.
Generally the low temperature fixing property and the grindability
of the resin at the time of toner production tend to be mutually
contradictory properties. As a toner excellent in the low
temperature fixing property and good in the grindability of the
resin at the time of toner production is disclosed a toner
containing a resin for a toner containing a specified amount of a
monovalent aliphatic compound having 10 to 24 carbon atoms as a
monomer component (reference to Patent Document No. 1).
Also, as an attempt to provide a toner that satisfies the low
temperature fixing property and is free from high temperature
offset, a toner having a loss tangent (tan .delta.) in a range from
1.0 or higher and lower than 2.0 in the case the loss modulus G''
is in a range from 1.times.10.sup.4 Pa to 1.times.10.sup.6 Pa, and
a loss tangent (tan .delta.) in a range from 0.5 or higher and
lower than 1.0 in the case the loss modulus G'' is 1.times.10.sup.3
Pa is disclosed (reference to Patent Document No. 2).
However, although the toner proposed in Patent Document No. 1 is
excellent in the low temperature fixing property, it is required to
be improved in both low temperature fixing property and
grindability for speed up and saving energy. Also, the toner
proposed in Patent Document No. 2 is good in the low temperature
fixing property and high temperature offset properties, however it
is insufficient to give satisfactory image quality for the use of
color images required to have luster.
To improve the moisture resistance and fixing capability of a
polyester toner, it is known that long chain aliphatic hydrocarbon
units are introduced into the main chains or side chains of
polyester resins by co-condensing tri- or higher valent polyhydric
alcohols with long chain aliphatic dicarboxylic acids or
dicarboxylic acids having long chain aliphatic side chains
(reference to Patent Document No. 3).
However, in these polyester resins, since sebacic acid or the like
is used as a long chain aliphatic dicarboxylic acid and
dodecenylsuccinic acid or the like as a dicarboxylic acid having a
long chain aliphatic side chain is used, the number of carbon atoms
of the aliphatic hydrocarbon unit to be introduced become so high
and although the moisture resistance and fixing property of a toner
are improved, the glass transition temperature (Tg) of the
polyester resins is lowered to lead to a problem that the storage
stability of a toner is deteriorated.
A toner for electrostatic image development to be used for a heat
fixing method is required to be not fuse with a heat roll even at a
high fixing temperature (hot offset resistance) and fixed even at a
low fixing temperature (low temperature fixing property). To
prevent hot offset, use of a wax is effective and to improve the
low temperature fixing property, it is effective to use a polyester
type resin as a binder for a toner.
However, compatibility of a wax and a polyester type resin is poor
and the dispersion particle diameter of the wax becomes large in a
toner. Accordingly, it results in fixing or filming of the wax on a
photoconductor to deteriorate image quality or charging failure to
deteriorate image quality. To solve these problems, Patent Document
No. 4 proposes use of graft polymers having a graft structure
formed by grafting styrene type polymer chains or styrene-(meth)
acrylic polymer chains to wax components. Accordingly, the wax
particle diameter in a toner is made controllable and toners which
are excellent in hot offset resistance and do not cause filming or
image deterioration are proposed.
However, the toners proposed in the Document are insufficient from
a viewpoint of the low temperature fixing property although being
effective in the hot offset resistance and causing no filming or
image deterioration.
As particles having uniform particle diameter and shape and
excellent in the electric property, thermal property, and chemical
stability have been known resin particles obtained by a suspension
method of removing organic solvents from suspensions of water-based
media and mixed solutions containing resins and the organic
solvents (reference to Patent Document No. 5).
However, with respect to resin particles to be used for heat fixing
method/heat processing method, they are further required to be
suitable for fixing and melting even at a low temperature from a
viewpoint of saving energy and the resin particles described in
Patent Document No. 5 are not necessarily sufficient as resins for
slush molding, a powder coating, an electrophotographic toner, an
electrostatic recording toner, an electrostatic printing toner, or
hot-melt adhesive. Patent Document No. 1: Japanese Patent Laid-Open
(JP-A) No. 2003-337443 Patent Document No. 2: JP-A No. 2003-280241
Patent Document No. 3: JP-A No. 62-78568 Patent Document No. 4:
JP-A No. 2001-134009 Patent Document No. 5: JP-A No.
2001-166538
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
An object of the invention is to provide resin particles for a
toner excellent in low temperature fixing property and having good
grindability of the resin at toner production.
Another object of the invention is to provide resin particles for a
toner also having good luster.
Another object of the invention is to provide resin particles for a
toner having good moisture resistance and fixing property when used
for a toner and giving excellent storage stability of a toner.
Another object of the invention is to provide a resin composition
for a toner giving a toner excellent in hot offset resistance
without inducing defective image formation and excellent in low
temperature fixing property.
Further, another object of the invention is to provide a
non-magnetic single component type toner excellent in low
temperature fixing property, grindability of the resin at toner
production, and excellent in luster and transparency as a color
toner.
Further, another object of the invention is to provide resin
particles excellent in fixing property and heat melting property
and having uniform particle diameter and shape by a suspension
method.
Means for Solving the Problems
The present inventors made studies of solution to this problem and
consequently have accomplished the invention.
That is, the invention includes the following 8 inventions: [1] a
polyester resin for a toner obtained by polycondensing a polyol
component and a polycarboxylic acid component, wherein the polyol
component has a molar average cohesive energy of 7.0.times.10.sup.4
to 1.4.times.10.sup.5 J and the polyester resin contains 20 to 100%
by weight of at least one kind of polyester resin (A1) having a
storage modulus in a range of 2.5.times.10.sup.3 Pa to
5.times.10.sup.6 Pa at 150.degree. C.; [2] a polyester resin for a
toner obtained by polycondensing a polyol component and a
polycarboxylic acid component, wherein the polyester resin contains
20 to 100% by weight of at least one kind of polyester resin (A2)
having a softening point in a range from 120.degree. C. to
180.degree. C. and a loss tangent of 0.9 or higher at a temperature
in a range from 130.degree. C. to 200.degree. C.; [3] a polyester
resin for a toner obtained by polycondensing a polyol component and
a polycarboxylic acid component, wherein the polycarboxylic acid
component comprises 80 to 100% by mole of terephthalic acid,
isophthalic acid, and/or a lower alkyl (carbon atoms of the alkyl:
1 to 4) ester of them (a); the polyol component comprises 20 to
100% by mole of an aliphatic diol (80 to 100% by mole of the
aliphatic diol is 1,2-propylene glycol) (b); and 0.1 to 20% by mole
of the total of the polyol component and the polycarboxylic acid
component are tri- or higher valent polyhydric alcohol and/or tri-
or higher valent polycarboxylic acid (c) and the polyester resin
has a softening point in a range from 95 to 160.degree. C. and a
glass transition temperature (Tg) in a range from 45 to 75.degree.
C.; [4] a polyester resin composition for a toner described in one
of [1] to [3] and an additive (B) for a toner comprising a modified
wax (w1) produced by modifying at least a part of a wax (w) with a
vinyl monomer (m); [5] a toner composition containing the polyester
resin for a toner as described in one of [1] to [3], a colorant,
and if necessary, one or more kinds of additives selected from the
group consisting of a release agent, a charge control agent, and a
fluidizing agent; [6] a non-magnetic single component toner to be
used in an image formation method of developing a latent image by
supplying a toner to a latent image carrier, wherein the toner
comprises the polyester resin for a toner (A1), (A2), or (A3) as
described in one of claims 1 to 3 and a colorant and has physical
properties within an area surrounded by straight lines defined by
the following equations (1) to (4) in xy-coordinates of glass
transition temperature (Tg) of (A1), (A2), or (A3) as a variant in
x-axis and softening point (sp) in y-axis, and one or more kinds of
fine particles additives being situated on the surface of the toner
particles. sp=4Tg-110, equation (1): sp=4Tg-170, equation (2):
sp=90, and equation (3): sp=130; equation (4): [7] a resin particle
comprising a resin (K) and an optional additive wherein the resin
particle is obtained by removing a solvent from a water-based
dispersion of (I) an oil based mixed solution containing at least
the resin (K) and an organic solvent and (II) a water-based medium,
wherein the resin (K) comprises one or more kinds of polyester
resins (K1) obtained by polycondensing a polyol component and a
polycarboxylic acid component and a tetrahydrofuran-soluble
fraction of the resin (s) (K1) has a number average molecular
weight of 1000 to 9500 and the polyol component comprises 85 to
100% by mole of an aliphatic diol having 2 to 6 carbon atoms or 70
to 100% by mole of 1,2-propylene glycol; and [8] a composite resin
particle comprising a resin particle (P) comprising a resin (p) and
an optional additive and a resin particle (Q) comprising a resin
(q) and an optional additive and adhering to the surface of the
resin particle (P), wherein the resin (p) comprises one or more
kinds of polyester resins (p1) obtained by polycondensing a polyol
component and a polycarboxylic acid component and the polyol
component comprises 85 to 100% by mole of an aliphatic diol having
2 to 6 carbon atoms or 70 to 100% by mole of 1,2-propylene glycol
and a tetrahydrofuran-soluble fraction of the resin(s) (p1) has a
number average molecular weight of 1000 to 9500, or the resin (p)
comprising a resin (p2) containing the resin (p1) as a component
unit.
Effects of the Invention
A toner excellent in low temperature fixing property can be
obtained by using the polyester resins for a toner and toner
composition of the first, second, and fifth inventions. Further,
since the grindability of the resin at toner production is
excellent, toner production is carried out economically at the time
industrial production. Further, since high temperature offset does
not occur at a temperature in a range from 130.degree. C. to
200.degree. C., the toner surface is kept smooth after fixing to
give an image with luster.
The polyester resin of the third invention is excellent in blocking
resistance, melt fluidity, low temperature fixing property, and
electrostatic property even in a high moisture condition. Further,
it has good resin properties even in the case no tin compound is
used as a catalyst.
A toner excellent in hot offset resistance without inducing
defective image formation and excellent in low temperature fixing
property can be obtained by using the polyester resin composition
of the fourth invention.
Use of the toner of the sixth invention gives excellent low
temperature fixing property and luster and transparency as a color
toner. Further, since the grindability of the resin at toner
production is excellent, toner production is carried out
economically at the time industrial production.
The resin particles of the seventh and eighth inventions have the
following effects: 1. excellent in low temperature melting property
and low temperature fixing property and thus saving energy
consumption at the time of melting process and printing; 2. having
uniform particle diameter and excellent in powder fluidity and
storage stability; 3. being obtained by dispersion in water and
thus produced at a low cost; and 4. having good heat resistance and
giving a coating with good mechanical properties.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing the relation between the glass transition
temperature (Tg) and the softening point (Sp) of a polyester resin
of the invention.
BEST MODES FOR CARRYING OUT THE INVENTION
Hereinafter, the invention will be described in detail.
The molar average cohesive energy of a polyol to be a component of
the polyester resin (A1) of the first invention is generally
7.0.times.10.sup.4 to 1.4.times.10.sup.5 J. The lower limit is
preferably 7.05.times.10.sup.4 J and more preferably
7.1.times.10.sup.4 J. The upper limit is preferably
1.25.times.10.sup.5 J and more preferably 1.times.10.sup.5 J. If
the molar average cohesive energy is 7.0.times.10.sup.4 J or
higher, thermal storage property is excellent and if it is
1.4.times.10.sup.5 J or lower, grindability is excellent.
The storage modulus of the resin (A1) consisting of the polyol
having the above-mentioned molar average cohesive energy at
150.degree. C. is generally in a range of 2.5.times.10.sup.3 Pa to
5.times.10.sup.6 Pa. The lower limit is preferably
3.0.times.10.sup.3 Pa and more preferably 3.2.times.10.sup.3 Pa and
the upper limit is preferably 4.5.times.10.sup.6 Pa and more
preferably 4.3.times.10.sup.6 Pa. If it is 2.5.times.10.sup.3 Pa or
higher, hot offset becomes excellent and if it is 5.times.10.sup.6
Pa lower, the low temperature fixing property becomes
excellent.
In the case two or more kinds of polyols are used, the component
mole ratio of respective polyols is calculated from the amounts of
used polyols and the amounts of recovered polyols at the time of
reaction.
With respect to the molar average cohesive energy, it is described
in Fedors et al, Polymer Engineering and Science, February, 1974,
vol. 14, No. 2, p. 147-154.
To adjust the molar average cohesive energy, since the cohesive
energy is an intrinsic value of each polyol, the mole ratio of
polyols should be controlled. To adjust the storage modulus of a
resin, for example, the molecular weight of the resin and the
number of crosslinking points should be adjusted.
A polyester resin (A1) of the first invention is preferably a
polyester resin (A2) of the second invention to be described later
and/or a polyester resin (A3) of the third invention to be
described later.
The softening point of the polyester resin (A2) of the second
invention is generally in a range from 120.degree. C. to
180.degree. C. The lower limit is preferably 125.degree. C. and
more preferably 130.degree. C. and the upper limit is preferably
175.degree. C. If the softening point is 120.degree. C. or higher,
the hot offset resistance is improved and if it is 180.degree. C.
or lower, the low temperature fixing property is improved.
In the invention, the softening point is measured by using a flow
tester CFT-500 manufactured by Shimadzu Corp., unless otherwise
specified, in the following isokinetic heating conditions and
defined as a point at which the flow rate becomes 1/2: Load: 20 kg,
Die: 1 mm.phi.-1 mm, and Heating speed: 6.degree. C./min.
The loss tangent of the resin (A2) at a temperature in a range from
130.degree. C. to 200.degree. C. is generally 0.9 or higher,
preferably 1.0 or higher, more preferably 1.02 or higher,
furthermore preferably 1.05 to 30, and even more preferably 1.1 to
20. The luster is improved with the loss tangent of 0.9 or
higher.
To adjust the softening point and loss tangent of the resin, for
example, the molecular weight of the resin and the number of
crosslinking points should be adjusted.
In the invention, the storage modulus and loss tangent of a
polyester resin is measured by the following elastic modulus
measurement apparatus: Apparatus: ARES-24A (Rheometric Ltd.), Tool;
25 mm parallel plates, Frequency: 20 Hz, Strain ratio: 5%, and
Heating speed: 5.degree. C./min.
The loss tangent in temperature in a range from 130.degree. C. to
200.degree. C. is read in a graph obtained by plotting the measured
values and showing the correlation between the temperature-loss
tangent.
The polyester resin (A2) of the second invention is preferably the
polyester resin (A1) of the first invention and/or the polyester
resin (A3) of the third invention.
The polyester resin (A1) or (A2) to be used in the first and second
invention is obtained generally by polycondensing at least one kind
of polyol components and at least one kind of polycarboxylic acid
components.
The polyol component to be used for the resin (A1) or (A2) is
preferable to comprise 30 to 100% by mole of an aliphatic diol
having 2 to 6 carbon atoms. Further, it is preferable that
1,2-propylene glycol is contained at least as a portion in the
diol. The content of the aliphatic diol having 2 to 6 carbon atoms
in the polyol component is more preferably 70 to 100% by mole,
furthermore preferably 85 to 100% by mole, even more preferably 90
to 100% by mole, and most preferably 100% by mole. If the content
is 30% by mole or higher, the resin strength becomes high and the
low temperature fixing property is improved.
Examples of the aliphatic diol having 2 to 6 carbon atoms are
alkane diols such as ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol,
1,5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol,
3,4-hexanediol, and neopentyl glycol and two or more of them may be
used in combination. Among them, ethylene glycol, 1,2-propylene
glycol, and neopentyl glycol are preferable; ethylene glycol and
1,2-propylene glycol are more preferable; and 1,2-propylene glycol
is furthermore preferable.
It is also preferable that the polyol component comprises 30 to
100% by mole of 1,2-propylene glycol and 0 to 30% by mole of
another polyol containing an aliphatic diol having 2 to 6 carbon
atoms other than 1,2-propylene glycol. In this case, the content of
1,2-propylene glycol in the polyol component is more preferably 70
to 100% by mole, furthermore preferably 85 to 100% by mole, even
more preferably 90 to 100% by mole, and most preferably 100% by
mole. If the content is 30% by mole or higher, the resin strength
becomes high and the low temperature fixing property is
improved.
The polyol component may contain polyhydric alcohols other than the
aliphatic diol having 2 to 6 carbon atoms.
Examples of dihydric alcohol (dialcohol) among the polyhydric
alcohols may include aliphatic diol having 7 to 36 carbon atoms
(e.g. 1,7-heptanediol and dodecanediol); polyalkylene ether glycol
having 4 to 36 carbon atoms (e.g. diethylene glycol, dipropylene
glycol, polyethylene glycol, and polypropylene glycol); adducts
(addition molar number 2 to 30) of alkylene oxides (hereinafter,
abbreviated as AO) [e.g. ethylene oxide (hereinafter, abbreviated
as EO) and propylene oxide (hereinafter, abbreviated as PO), and
butylene oxide] having 2 to 4 carbon atoms and aliphatic diols
having 2 to 6 and 7 to 36 carbon atoms; alicyclic diol having 6 to
36 carbon atoms (e.g. 1,4-cyclohexan dimethanol, hydrogenated
bisphenol A); adducts (addition molar number 2 to 30) of AO having
2 to 4 carbon atoms to alicyclic diols; and adducts (addition molar
number 2 to 30) of AO having 2 to 4 carbon atoms to bisphenols
(e.g. bisphenol A, bisphenol F, and bisphenol S).
Examples of tri- to octa-hydric or higher hydric alcohols among the
polyhydric alcohols are aliphatic tri- to octa-hydric or higher
hydric alcohols having 3 to 36 carbon atoms (e.g. glycerin,
triethylolethane, trimethylolpropane, pentaerythritol, sorbitol,
1,2,4-butane-triol, 2-methyl-1,2,3-propanetriol,
2-methyl-1,2,4-butanetriol, 1,2,5-pentanetriol, and
1,3,5-trihydroxymethylbenzene); adducts (addition molar number 2 to
30) of AO having 2 to 4 carbon atoms to the above-mentioned
aliphatic polyhydric alcohols; adducts (addition molar number 2 to
30) of AO having 2 to 4 carbon atoms to trisphenols (e.g.
trisphenol PA); and adducts (addition molar number 2 to 30) of AO
having 2 to 4 carbon atoms to novolak resins (e.g. phenol novolak
and cresol novolak; average polymerization degree of 3 to 60).
Preferable examples among them are polyalkylene ether glycol having
4 to 36 carbon atoms, alicyclic diols, adducts of AO having 2 to 4
carbon atoms to alicyclic diols having 6 to 36 carbon atoms,
adducts of AO having 2 to 4 carbon atoms to bisphenols, adducts of
AO having 2 to 4 carbon atoms to novolak resins; and more
preferable examples are adducts of AO having 2 to 3 carbon atoms
(EO and PO) to bisphenols and adducts of AO having 2 to 3 carbon
atoms (EO and PO) to novolak resins.
Examples of the aliphatic (including alicyclic) dicarboxylic acids
as the polycarboxylic acid component are alkanedicarboxylic acids
having 2 to 50 carbon atoms (e.g. oxalic acid, malonic acid,
succinic acid, adipic acid, lepargylic acid, and sebacic acid) and
alkenedicarboxylic acids having 4 to 50 carbon atoms (e.g.
alkenylsuccinic acid such as dedecenylsuccinic acid, maleic acid,
fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and
glutaconic acid).
Examples of the aromatic dicarboxylic acids are aromatic
dicarboxylic acids having 8 to 36 carbon atoms (e.g. phthalic acid,
isophthalic acid, terephthalic acid, and naphthalenedicarboxylic
acid).
Examples of the aliphatic (including alicyclic) tri- to hexa- or
higher valent polycarboxylic acids as the polycarboxylic acid
component are aliphatic tricarboxylic acids having 6 to 36 carbon
atoms (e.g. hexanetricarboxylic acid) and vinyl polymers of
unsaturated carboxylic acids [number average molecular weight
(hereinafter abbreviated as Mn) measured by gel permeation
chromatography (GPC): 450 to 10000] (e.g. .alpha.-olefin/maleic
acid copolymers).
Examples of the tri- to hexa- or higher aromatic polycarboxylic
acids as the polycarboxylic acid component are aromatic
polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid
and pyromellitic acid) and vinyl polymers of unsaturated carboxylic
acids [Mn: 450 to 10000] (e.g. styrene/maleic acid copolymers,
styrene/acrylic acid copolymers, and styrene/fumaric acid
copolymers).
As the polycarboxylic acid component are usable anhydrides and
lower alkyl (having 1 to 4 carbon atoms) esters (methyl esters,
ethyl esters, and isopropyl esters) of these polycarboxylic
acids.
Preferable examples among these polycarboxylic acid components are
alkanedicarboxylic acids having 2 to 50 carbon atoms,
alkenedicarboxylic acids having 4 to 50 carbon atoms, aromatic
dicarboxylic acids having 8 to 20 carbon atoms, and aromatic
polycarboxylic acids having 9 to 20 carbon atoms; more preferable
examples are adipic acid, alkenylsuccinic acid having 16 to 50
carbon atoms, terephthalic acid, isophthalic acid, maleic acid,
fumaric acid, trimellitic acid, pyromellitic acid, and combinations
of these acids; even more preferable examples are adipic acid,
terephthalic acid, trimellitic acid, and combinations of these
acids. Anhydrides and lower alkyl esters of these acids are also
preferable.
Further, as the polycarboxylic acid component, those consisting of
an aromatic polycarboxylic acid and an aliphatic polycarboxylic
acid and having a content of the aromatic polycarboxylic acid in a
range of 60% by mole or higher are preferable. The lower limit of
the content of the aromatic polycarboxylic acid is more preferably
70% by mole and even more preferably 80% by mole, and upper limit
is preferably 99% by mole and even more preferably 98% by mole. If
the content of the aromatic polycarboxylic acid is 60% by mole or
higher, the resin strength is increased and the low temperature
fixing property is further improved.
The polyester resin (A3) for a toner of the third invention is
obtained by polycondensing one or more kinds of polyol components
and one or more polycarboxylic acid components and the
polycarboxylic acid component comprises 80 to 100% by mole of
terephthalic acid, isophthalic acid, and/or a lower alkyl (carbon
atoms of the alkyl: 1 to 4) ester of them (a); the polyol component
comprises 20 to 100% by mole of an aliphatic diol (80 to 100% by
mole of the aliphatic diol is 1,2-propylene glycol) (b); and 0.1 to
20% by mole of the total of the polyol component and the
polycarboxylic acid component are tri- or higher valent polyhydric
alcohol and/or tri- or higher valent polycarboxylic acid (c).
The polyester resin (A3) for a toner of the third invention is also
preferably the polyester resin (A1) of the first invention and/or
the polyester resin (A2) of the second invention.
The above-mentioned (a) means terephthalic acid, isophthalic acid,
and/or a lower alkyl (carbon atoms of the alkyl: 1 to 4) ester of
them and that the esters of lower alkyl having 1 to 4 carbon atoms
includes hydroxyalkyl esters.
Practical examples of the lower alkyl ester are dimethyl
terephthalate, dimethyl isophthalate, diethyl terephthalate,
diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate,
terephthalic acid propylene glycol diester, and isophthalic acid
propylene glycol diester. Among of (a), in terms of the reaction
speed and cost, terephthalic acid, isophthalic acid, dimethyl
terephthalate, dimethyl isophthalate, terephthalic acid propylene
glycol diester and isophthalic acid propylene glycol diester are
preferable.
Since the component (a) has an effect to increase the glass
transition temperature (hereinafter, referred to as Tg) of the
polyester resin to be obtained and thereby improve the blocking
resistance of a toner, it is contained in a range generally from 80
to 100% by mole, preferably from 85 to 100% by mole, and even more
preferably from 90 to 100% by mole in the total polycarboxylic acid
component.
Examples usable as a dicarboxylic acid other than (a) in the
polycarboxylic acid component composing the polyester resin are the
above exemplified alkane dicarboxylic acids having 2 to 50 carbon
atoms, alkene dicarboxylic acids having 4 to 50 carbon atoms,
aromatic dicarboxylic acid having 8 to 36 carbon atoms other than
(a) (e.g. naphthalenedicarboxylic acid); anhydrides and lower alkyl
(having 1 to 4 carbon atoms) esters [e.g. phthalic acid
(anhydride)]. They may be used alone or two or more kinds of them
may be used in combination.
In the third invention, the aliphatic diol (b) includes the
above-mentioned aliphatic diols having 2 to 6 carbon atoms, the
above-mentioned aliphatic diols having 7 to 36 carbon atoms,
polyalkylene ether glycol having 4 to 36 carbon atoms; adducts of
AO having 2 to 4 carbon atoms to the aliphatic diols having 2 to 6
and 7 to 36 carbon atoms; alicyclic diols having 3 to 36 carbon
atoms; and adducts of AO having 2 to 4 carbon atoms to the
alicyclic diols and they may be used alone or two or more of them
may be used in combination.
Particularly, in terms of the balance between the fixing property
of a toner and environment-dependency, it is preferably that 80% by
mole or more of the aliphatic diol to be used is 1,2-propylene
glycol. As other aliphatic diols other than 1,2-propylene glycol
are preferably ethylene glycol, 1,4-butanediol, neopentyl glycol,
and 1,4-cyclohexanedimethanol. Since these diols as (b) have an
effect to lower the melt viscosity of the polyester resin, the
fixing property of the toner is improved. The content is preferably
20 to 100% by mole, more preferably 45 to 100% by mole, furthermore
preferably 60 to 100% by mole, and most preferably 70 to 100% by
mole in the total of the polyol component. If the content of (b) is
20% by mole or higher, the fixing property of the toner is made
excellent and decrease of the moisture resistance is
suppressed.
As a diol other than (b) in the polyol component composing the
polyester resin are exemplified the above-mentioned adducts of AO
having 2 to 4 carbon atoms to bisphenols.
Examples of the tri- or higher (tri- to octa- or higher) polyhydric
alcohol and/or tri- or higher (tri- to octa- or higher)
polycarboxylic acid (c) may include the above exemplified tri- to
octa- or higher hydric aliphatic polyalcohols having 3 to 36 carbon
atoms; adducts of AO having 2 to 4 carbon atoms to the
above-mentioned aliphatic polyalcohols; adducts of AO having 2 to 4
carbon atoms to the above-mentioned trisphenols; adducts of AO
having 2 to 4 carbon atoms to the above-mentioned novolak resins;
aliphatic tricarboxylic acids having 3 to 36 carbon atoms; the
above-mentioned unsaturated carboxylic acid vinyl polymers; tri- to
hexa- or higher valent polycarboxylic acids having 9 to 20 carbon
atoms; and the above-mentioned unsaturated carboxylic acid vinyl
polymers.
Preferable examples among them are adducts (average addition mole:
2 to 30) of AO having 2 to 4 carbon atoms to the novolak resins;
tri- to hexa- or higher aromatic polycarboxylic acids having 9 to
20 carbon atoms (e.g. trimellitic acid and pyromellitic acid) and
more preferable examples are adducts (average addition mole: 2 to
30) of AO (particularly EO and/or PO) having 2 to 4 carbon atoms to
the novolak resins. These compounds may be used alone or two or
more of them may be used in combination. These compounds (c) have
an effect to increase non-offset property of a toner by
crosslinking or branching the polyester resin.
The content of (c) is preferably 0.1 to 20% by mole, more
preferably 0.5 to 18% by mole, in the total of the polyol component
and polycarboxylic acid component. If it is controlled to be 0.1%
or higher by mole, a polyester resin having a viscosity and Tg in
respectively proper ranges can be obtained and thus both non-offset
property and storage stability of the toner are made sufficient. If
it is controlled to be 20% or lower by mole, crosslinking of the
polyester resin is prevented in a viscosity equal to or lower than
the proper range and thus the non-offset range can be widened.
In the third invention, unless the properties of the polyester
resin are not deteriorated, other monomers, e.g. monocarboxylic
acids such as benzoic acid, p-substituted benzoic acid,
o-substituted benzoic acid, acetic acid, propionic acid, butyric
acid, and their methyl and ethyl esters and anhydrides; mono-ols
such as benzyl alcohol, p-substituted benzyl alcohol, o-substituted
benzyl alcohol, lauryl alcohol, myristyl alcohol, and stearyl
alcohol; and hydroycarboxylic acid derivatives such as
.epsilon.-caprolactone, methylvarelolactone and its ring-opening
polymers, can be used in a range of 10% by mole or less in the
total of the polyol component and polycarboxylic acid
component.
The polyester resin of the third invention obtained by
polycondensing the above-mentioned components has a softening point
in a range generally from 95 to 160.degree. C., preferably
100.degree. C. in the lower limit and 150.degree. C. in the upper
limit, and more preferably lower than 120.degree. C. and Tg in a
range generally from 45 to 75.degree. C., preferably 50.degree. C.
in the lower limit and 70.degree. C. in the upper limit.
If the softening point is controlled to be 95.degree. C. or higher,
the toughness of the polyester resin becomes preferable and on the
other hand, if it is controlled to be 160.degree. C. or lower, the
melt fluidity and the low temperature fixing property of the toner
can be made desirable.
If Tg is controlled to be 45.degree. C. or higher, the blocking
resistance of the toner is made preferable and if it is controlled
to be 75.degree. C. or lower, the fixing property of the toner is
made desirable.
Tg is measured by a method (DSC method) as standardized in ASTM
D3418-82 by DSC 20, SSC/580 manufactured by Seiko Instruments
Inc.
The polyester resin (A1) to (A3) in the invention may be produced
by a common polyester production method. For example, the
production method may be carried out in an inert gas (e.g. nitrogen
gas or the like), at a reaction temperature preferably 150 to
280.degree. C., more preferably 160 to 250.degree. C., and even
more preferably 170 to 235.degree. C. The reaction time is
preferably 30 minute or longer and particularly preferably 2 to 40
hours in terms of reliable performance of polycondensation.
In this case, if necessary, an esterification catalyst may be used.
Examples of the esterification catalyst are tin-containing
catalysts (e.g. dibutyltin oxide, dioctyltin oxide, dictyltin
dilaurate), antimony-containing catalysts (e.g. antimony trioxide),
titanium-containing catalysts (e.g. titanium alkoxide, potassium
titanyl oxalate, titanium terephthalate), zirconium-containing
catalysts (e.g. zirconyl acetate), nickel-containing catalysts
(e.g. nickel acetyl acetate), aluminum-containing catalysts (e.g.
aluminum hydroxide and aluminum triisopropoxide), zinc acetate, and
manganese acetate. Among them, in terms of the reactivity and
environmental hygiene, catalyst containing one or more metals
selected from titanium, antimony, zirconium, nickel, and aluminum
are preferable. It is also effective to reduce the pressure in
order to improve the reaction speed in the terminal period of the
reaction.
It is preferable to determine an addition amount of the catalyst so
properly as to make the reaction speed maximum. The addition amount
is preferably 10 ppm to 1.9% and more preferably 100 ppm to 1.7% in
the entire raw materials. If the addition amount is 10 ppm or
higher, the reaction speed is increased and therefore it is
preferable. Hereinafter, % means % by weight, unless otherwise
specified.
The reaction ratio of the polyol component and the polycarboxylic
acid component in the case of production of polyester resin (A1) to
(A3) of the first to the third invention [hereinafter, collectively
referred to as (A) for (A1) to (A3)] is preferably (2/1) to (1/2),
more preferably (1.5/1) to (1/1.3), and even more preferably
(1.3/1) to (1/1) on the basis of equivalent ratio [OH]/[COOH] of
the hydroxyl groups and carboxyl groups.
The Mn of a tetrahydrofuran (THF)-soluble fraction of the resin (A)
is preferably in a range from 1000 to 9500, more preferably in a
range from 1200 to 9300, and even more preferably in a range from
1400 to 9100. If Mn is 1000 or higher, the resin strength is
increased and if it is 9500 or lower, the low temperature fixing
property and grindability of the resin are improved.
The peak top molecular weight (hereinafter, referred to as Mp) of
the THF-soluble fraction of the resin (A) is preferably in a range
from 1200 to 50000 and more preferably in a range from 1500 to
40000 in terms of the balance among the resin strength, low
temperature fixing property, and grindability of the resin.
The amount of components with a molecular weight of 500 or less in
a chromatogram by gel permeation chromatography of the THF-soluble
fraction of the resin (A) is preferably 3% or less and more
preferably 2.5% or less. If the amount of components with a
molecular weight of 500 or less is 3% or less, in the case the
resin (A) is used as a toner, the fluidity is further improved and
the image stability is improved at the time of continuous printing.
In the case of using two or more kinds of resins as the resin (A),
even in the case a resin with a high quantity of the components
with a molecular weight of 500 or less is contained, if the amount
is within the above-mentioned range in the entire body of the resin
(A), it is preferable.
The Mn, Mp, and the amount of the components with a molecular
weight of 500 or lower of the THF-soluble fraction in the polyester
resin are measured by GPC in the following conditions. Apparatus:
HLC-8120, manufactured by Tosho Corp., Column: TSK GEL GMH6 2
columns, manufactured by Tosho Corp., Measurement temperature:
40.degree. C., Sample solution: 0.25% THF solution, Injection
amount of solution: 100 .mu.L, Detection apparatus: refractive
index detector, and Standard substance: standardized
polystyrenes
The molecular weight at the maximum peak height in the obtained
chromatogram is named as the peak top molecular weight (Mp). The
amount of the components with a molecular weight of 500 or lower is
calculated by integration from 0 to 500 in the molecular weight
distribution list. To carry out the measurement, one optional
particle is selected among resin particles and dissolved in THF to
obtain a sample solution. Such measurement of the sample solution
is carried out for 10 particles.
Tg of the polyester resin (A1) and (A2) of the first and second
inventions is preferably in a range from 40 to 90.degree. C., more
preferably in a range from 45 to 85.degree. C., and even more
preferably in a range from 50 to 80.degree. C. in terms of the
thermal storage property and low temperature fixing property.
THF-insoluble fraction in the resin (A) is preferably 70% or less
in terms of the low temperature fixing property. The lower limit is
more preferably 1%, even more preferably 2%, or most preferably 3%
and the upper limit is more preferably 40% and even more preferably
30%.
The above-mentioned THF-insoluble fraction is measured by the
following method. At first, 0.5 g of a sample is added to 50 ml of
THF and the obtained solution is stirred and refluxed for 3 hours.
After cooling, the insoluble fraction is separated by filtration
with a glass filter and the resin component on the glass filter is
vacuum-dried at 80.degree. C. for 3 hours. The insoluble fraction
is calculated from the weight ratio of the weight of the dried
resin on the glass filter and the weight of the sample.
Hydroxy value (mgKOH/g) of the resin (A) is preferably 70 or lower,
more preferably in a range from 5 to 40, and even more preferably
in a range from 10 to 30. If the hydroxyl value is 70 or lower, the
environment stability and the amount of the electrostatic charge
are improved. Acid value (mgKOH/g) of the resin (A) is preferably
40 or lower, more preferably in a range from 1 to 30, and even more
preferably in a range from 2 to 25, and most preferably 5 to 20. If
the acid value is 40 or lower, the environment stability is
improved. If the resin has a proper acid value, the rising up of
charging is improved and thus it is preferable.
Two or more kinds of the polyester resin (A) of the invention may
be used in combination and in terms of attainment of both
satisfactory low temperature fixing property and hot offset
resistance, respectively one or more kinds of linear polyester
resins (Aa) and non-linear polyester resins (Ab) may be used in
combination.
A linear polyester resin (Aa) is generally obtained by
polycondensing the above-mentioned diol and dicarboxylic acid. It
may be modified in the molecule terminals with an anhydride of the
above-mentioned polycarboxylic acids (including tri- or higher
valent polycarboxylic acids).
A non-linear polyester resin (Aa) is generally obtained by reaction
of the above-mentioned dicarboxylic acid and diol as well as the
above-mentioned tri- or higher valent polycarboxylic acids and/or
tri- or higher hydric polyalcohols.
Examples of the tri- or higher valent polycarboxylic acids and/or
tri- or higher hydric polyalcohols are preferably adducts (average
addition molar number 2 to 30) of AO having 2 to 4 carbon atoms to
novolak resins, tri- to hexa- or higher aromatic polycarboxylic
acids having 9 to 30 carbon atoms (e.g. trimellitic acid and
pyromellitic acid) and more preferably tri- to hexa- or higher
aromatic polycarboxylic acids.
With respect to the ratio of the tri- or higher valent
polycarboxylic acids and tri- or higher hydric polyalcohols in the
case of obtaining the resin (Ab), the total of the moles of them in
the total moles of the polyol components and the polycarboxylic
acid components is preferably in a range from 0.1 to 40% by mole,
more preferably in a range from 1 to 25% by mole, and even more
preferably in a range from 3 to 20% by mole.
The THF-insoluble fraction of the resin (Aa) is preferably 3% or
less, more preferably 1% or less, and even more preferably 0%. As
the THF-insoluble fraction of the resin (Aa) is less, it is more
preferable in terms of the low temperature fixing property.
The THF-insoluble fraction of the resin (Ab) is preferably 1 to
70%. The lower limit is more preferably 2% and even more preferably
5% and an upper limit is more preferably 60% and even more
preferably 50%. Including the THF-insoluble fraction within the
above-mentioned range is preferable in terms of the improvement of
the hot offset resistance.
The polyester resin for a toner of the invention may contain other
polyester resins to an extent that the properties of the polyester
resin (A) are not deteriorated. Examples of other polyester resins
are polyester resins having Mn in a range from 1000 to 1,000,000,
more preferably in a range from 1000 to 9500 other than resins (A1)
to (A3). If the resin (A) is the non-linear polyester resin (Ab),
another resin to be used in combination is preferably a linear
polyester resin other than the resin (Aa).
The content of (A) in the polyester resin is in a range generally
from 20 to 100%, preferably from 25 to 100%, and even more
preferably from 30 to 90%. If it is 20% or higher, the properties
of the invention are sufficiently exhibited.
The polyester resin for a toner of the fourth invention contains
the above-mentioned polyester resin (A) for a toner and an additive
(B) for a toner comprising a modified wax (w1) produced by
modifying at least a part of a wax (w) with a vinyl monomer
(m).
The wax (w) to be used as a starting material of the additive (B)
may include polyolefin waxes, natural waxes, aliphatic alcohols
having 30 to 50 carbon atoms, fatty acids having 30 to 50 carbon
atoms, and their mixtures.
Examples of the polyolefin waxes are (co)polymers [obtained by
(co)polymerization and including thermal degradation polyolefins]
ofolefins (e.g. ethylene, propylene, 1-butene, isobutylene,
1-hexene, 1-dodecene, 1-octadecene, and their mixture); oxides of
(co)polymers by oxygen or oxone; maleic acid-modified products of
olefin (co)polymers [e.g. products modified with maleic acid and
its derivatives (e.g. maleic anhydride, monomethyl maleate,
monobutyl maleate, and dimethyl maleate)]; copolymers of olefin
with unsaturated carboxylic acids [e.g. (meth)acrylic acid,
itaconic acid, and maleic anhydride] and/or unsaturated carboxylic
acid alkyl esters [e.g. (meth)acrylic acid alkyl (alkyl having 1 to
18 carbon atoms) esters and maleic acid alkyl (alkyl having 1 to 18
carbon atoms) esters]; and sasol waxes.
In terms of the filming to a carrier and releasing property, Mn of
the polyolefin waxes is preferably in a range from 400 to 40000,
more preferably from 1000 to 30000, and even more preferably 1500
to 2000.
Examples of the natural waxes are carnauba wax, montan wax,
paraffin wax, and rice wax. Aliphatic alcohols having 30 to 50
carbon atoms may include triacontanol. Fatty acids having 30 to 50
carbon atoms may include triacontanecarboxylic acid.
Preferable examples among them are polyolefin waxes, natural waxes,
and their mixtures, furthermore preferable examples are thermal
degradation polyolefins, and even more preferable examples are
thermal degradation polyethylene and thermal degradation
polypropylene.
The softening point of the wax (w) is preferably in a range from 50
to 170.degree. C. The lower limit is more preferably 80.degree. C.,
furthermore preferably 90.degree. C., and even more preferably
100.degree. C. and the upper limit is more preferably 160.degree.
C. and even more preferably 155.degree. C. If the softening point
is 50.degree. C. or higher, the fluidity of the toner is good and
if it is 170.degree. C. or lower, a sufficient releasing effect can
be obtained.
The softening point is measured by a method standardized in JIS K
2207-1996.
In terms of the fixing property of the toner, the melt viscosity of
the wax (w) is generally in a range from 2 to 10000 mPas,
preferably from 3 to 7000 mPas, and more preferably from 5 to 4500
mPas at 160.degree. C.
In terms of the developing property of the toner, the pin
penetration degree of the wax (w) is generally 5.0 or lower,
preferably 3.5 or lower, and more preferably 1.0 or lower.
The pin penetration degree is measured by a method standardized in
JIS K 2207-1996.
Examples usable as the vinyl monomer (m) are following monomers (a)
to (f) and combinations of them: (a) carboxyl-containing vinyl
monomers: (a-1) unsaturated monocarboxylic acids having 3 to 20
carbon atoms: e.g. (meth)acrylic acid, crotonic acid, and cinnamic
acid; (a-2) unsaturated dicarboxylic acids having 4 to 30 carbon
atoms and their ester-forming derivatives [acid anhydrides and
mono- or di-alkyl (alkyl having 1 to 18 carbon atoms) esters]: e.g.
maleic acid, fumaric acid, itaconic acid, citraconic acid, and
their anhydrides and mono- or di-alkyl (alkyl having 1 to 18 carbon
atoms) esters (e.g. methyl esters and ethyl esters); (a-3) alkyl
(alkyl having 1 to 24 carbon atoms) esters of unsaturated
carboxylic acids having 3 to 30 carbon atoms: e.g. methyl
(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl
(meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate,
heptadecyl (meth)acrylate, eicoxyl (meth)acrylate,
cyclohexyl(meth)acrylate, benzyl (meth)acrylate,
phenyl(meth)acrylate, and ethyl-.alpha.-ethoxy-(meth)acrylate;
(a-4) polyhydric (di- and tri-) alcohol esters of unsaturated
carboxylic acids having 3 to 30 carbon atoms: e.g. ethylene glycol
di(meth)acrylate, propyleneglycol di(meth)acrylate, neopentyl
glycol di(meth)acrylate, trimethylol propane tri(meth)acrylate,
1,6-hexanediol diacrylate, and polyethylene glycol
di(meth)acrylate; and (a-5) esters of unsaturated alcohols (e.g.
vinyl and isopenyl) and polycarboxylic acids having 1 to 12 carbon
atoms: e.g. vinyl acetate, vinyl butylate, vinyl propionate, vinyl
butyrate diallylphthalate, diallyl adipate, isopropenyl acetate,
methyl 4-vinylbenzoate, vinyl methoxyacetate, and vinyl benzoate:
(b) hydroxyl-containing vinyl monomers: (b-1) hydroxyalkyl
(meth)acrylate having 5 to 16 carbon atoms, e.g. hydroxyethyl
(meth)acrylate and hydroxypropyl (meth)acrylate; (b-2) alkenols
having 2 to 12 carbon atoms, e.g. (meth)allylalcohol, 1-buten-3-ol
and 2-buten-1-ol; (b-3) alkenediols having 4 to 12 carbon atoms,
e.g. 2-butene-1,4-diol; and (b-4) alkenyl ethers having 3 to 30
carbon atoms, e.g. 2-hydroxyethylpropenyl ether and sucrose allyl
ether: (c) vinyl hydrocarbons: (c-1) aromatic vinyl hydrocarbons (8
to 20 carbon atoms) such asstyrene; e.g. hydrocarbonyl (e.g. alkyl,
cycloalkyl, aralkyl, and/or alkenyl)-substituted styrene such as
.alpha.-methylstyrene, vinyltoluene, 2,4-dimethylstyrene,
ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene,
cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene,
divinyltoluene, divinylxylene, and trivinylbenzene; and
vinylnaphthalene; (c-2) aliphatic vinyl hydrocarbons; e.g. alkenes
having 2 to 20 carbon atoms such as ethylene, propylene, butene,
isobutene, pentene, heptene, diisobutylene, octene, dodecene,
octadecene, and .alpha.-olefins other than exemplified above;
alkadienes having 4 to 20 carbon atoms such as butadiene, isoprene,
1,4-pentadiene, 1,5-hexadiene, and 1,7-octadiene; (c-3) alicyclic
vinyl hydrocarbons; e.g. mono-di-cycloalkenes and alkadienes such
as cyclohexene, (di)cyclopentadiene, vinylcyclohexene, and
ethylidenebicycloheptene; terpenes such as pinene, limonene, and
indene: (d) epoxy-containing vinyl monomers: e.g. glycidyl
(meth)acrylate: (e) nitrile group-containing vinyl monomers: e.g.
(meth)acrylonitrile: and (f) amino group-containing vinyl monomers:
e.g. aminoethyl (meth)acrylate, diemethylaminoethyl (meth)acrylate,
diethylaminoethyl (meth)acrylate, tert-butylaminoethyl
(meth)acrylate, N-aminoethyl (meth)acrylamide, (meth)acrylamine,
morpholinoethyl (meth)acrylate, 4-vinylpyridine, 2-vinylpyridine,
crotylamine, methyl .alpha.-acetaminoacrylate, vinylimidazole,
N-vinylpyrrole, and N-vinylthiopyrrolidone.
Preferable examples among them are styrene and styrene in
combination with other monomers [preferably (a) and (b),
particularly preferably (a-3) and (b-1)].
The modified wax (w1) is obtained by modifying the wax (w) with a
vinyl monomer (m) and the additive (B) for a toner to be used in
the invention may contain a wax (w) which is not reacted and/or a
copolymer of the monomer (m) in addition to the modified wax (w1)
grafted with the monomer (m).
The weight ratio of the wax (w) and the monomer (m) at the time of
producing the modified wax (w1) is preferably (1 to 30): (70 to 99)
and more preferably (2 to 27): (83 to 98) in terms of the fluidity
of the toner to be obtained.
Tg of the modified wax (w1) is preferably in a range from 40 to
90.degree. C., more preferably in a range from 50 to 80.degree. C.,
and even more preferably in a range from 55 to 75.degree. C. If Tg
is in a range from 40.degree. C. to 90.degree. C., the thermal
storage stability and low temperature fixing property are
excellent.
Mn of the modified wax (w1) is preferably in a range from 2000 to
10000 and more preferably in a range from 2500 to 9000. If Mn is
within a range from 2000 to 10000, the durability and grindability
of the toner to be obtained are excellent.
The additive (B) for a toner containing the modified wax (w1) is
obtained, for example, by dissolving or dispersing a wax (w) in a
solvent (e.g. toluene or xylene), heating to 100-200.degree. C.,
successively carrying out polymerization by dropwise adding the
monomer (m) and a peroxide type initiator (e.g. benzoyl peroxide,
di-tert-butyl peroxide, or tert-butyl peroxide benzoate), and then
removing the solvent.
The amount of the peroxide type initiator is generally 0.2 to 10%
and preferably 0.5 to 5% in the total weight of the wax (w) and
monomer (m).
The resin composition for a toner of the fourth invention comprises
the polyester resin (A) and the additive (B) for a toner. The weigh
ratio of the resin (A) and the additive (B) is preferably (25 to
99.9): (0.1 to 75), more preferably (50 to 99): (1 to 50), and even
more preferably (75 to 98): (2 to 25) in order to control the wax
particle diameter in the toner.
In addition, the polyester resin composition for a toner of the
invention may contain, based on the necessity, other resins and a
release agent, which will be described later, besides the polyester
resin (A) and additive (B). In the invention, the additive (B) for
a toner has a function as a compatibility-improving agent for
improving the compatibility of the polyester resin with the release
agent.
To obtain the polyester resin composition for a toner of the fourth
invention, the additive (B) for a toner and the polyester resin (A)
may be mixed in the form of powders or in the form of melts by a
biaxial extruder or a mixing pot capable of heating and stirring
and the additive (B) for a toner may be produced in the presence of
polyester resin (A).
The toner composition of the fifth invention contains the polyester
resin (A) for a toner to be a binder resin, a colorant, and if
necessary, one or more kinds of additives such as a release agent,
a charge control agent, and a fluidizing agent.
All kinds of dyes and pigments used as a coloring agent for a toner
may be used as the colorant. Practically, examples are carbon
black, iron black, Sudan black SM, First Yellow G, Benzidine
Yellow, Pigment Yellow, Indian First Orange, Irgasin Red,
p-Nitoaniline Red, Toluidine Red, Carmine FB, Pigment Orange R,
Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake,
Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine
Green, Oil Yellow GG, Kayaset YG, Orazol Brawn B, and Oil Pink OP
and these dyes may be used alone or two or more of them may be used
in form of a mixture. Further, if necessary, a magnetic powder (a
powder of a ferromagnetic metal such as iron, cobalt, and nickel or
a compound such as magnetite, hematite, and ferrite) may be added
for a function as a colorant. The content of the colorant is
preferably in a range from 1 to 40 part and more preferably in a
range from 3 to 10 part to 100 part of the polyester resin of the
invention. In the case of using the magnetic powder, it is
preferably in a range from 20 to 150 part and more preferably in a
range from 40 to 120 part. "Part" in the specification means part
by weight.
As the release agent, those having a softening point from 50 to
170.degree. C. are preferable and examples are polyolefin waxes,
natural waxes, aliphatic alcohols having 30 to 50 carbon atoms,
fatty acids having 30 to 50 carbon atoms, and their mixtures.
Practical examples are those same as exemplified for the
above-mentioned wax (w).
Examples of the natural waxes are carnauba wax, montan wax,
paraffin wax, and rice wax. The aliphatic alcohols having 30 to 50
carbon atoms may include triacontanol. Fatty acids having 30 to 50
carbon atoms may include triacontanecarboxylic acid.
Examples of the charge control agent are Nigrosine dyes,
triphenylmethane type dies having tertiary amines in side chains,
quaternary ammonium salts, polyamine resins, imidazole derivatives,
quaternary ammonium salt-containing polymers, metal-containing azo
dyes, copper-phthalocyanine dyes, metal salicylate, boron benzylic
acid complexes, sulfonic acid group-containing polymers,
fluorine-containing polymers, and halogen-substituted aromatic
ring-containing polymers.
Examples of the fluidizing agent are colloidal silica, alumina
powder, titanium oxide powder, and calcium carbonate powder.
With respect to the component ratio of the toner composition of the
fifth invention, based on the toner weight, the ratio of the
polyester resin of the invention is preferably in a range from 30
to 97%, more preferably from 40 to 95%, and even more preferably
from 45 to 92%; the ratio of the colorant is preferably in a range
from 0.05 to 60%, more preferably from 0.1 to 55%, and even more
preferably from 0.5 to 50%; and with respect to the additives, the
ratio of the release agent is preferably in a range from 0 to 30%,
more preferably from 0.5 to 20%, and even more preferably from 1 to
10%; the ratio of the charge control agent is preferably in a range
from 0 to 20%, more preferably from 0.1 to 10%, and even more
preferably from 0.5 to 7.5%; the ratio of the fluidizing agent is
preferably in a range from 0 to 10%, more preferably from 0 to 5%,
and more preferably from 0.1 to 4%. The total content of these
additives is preferably in a range from 3 to 70%, more preferably
from 4 to 58%, and even more preferably from 5 to 50%. If the
component ratios of the toner are within the above-mentioned
ranges, it becomes easy to obtain a toner with excellent
electrostatic property.
The toner composition of the invention may be obtained by any
conventionally known method such as a kneading and grinding method,
an emulsifying phase-inversion method, and a polymerization. For
example, in the case of obtaining a toner by the kneading and
grinding method, components composing the toner except a fluidizing
agent are dry-blended and successively melted and kneaded and then
the melted mixture is roughly grinded and finally finely granulated
by jet mill pulverizer and further the granulated powder is
classified to obtain fine particles having a particle diameter
(D50) preferably in a range from 5 to 20 .mu.m and then the
fluidizing agent is added to the particles to obtain a toner. The
particle diameter (D50) is measured by a Coulter Counter (trade
name: Multisizer III, manufactured by Coulter Co.).
In the case of obtaining a toner by the emulsifying phase-inversion
method, components composing the toner except a fluidizing agent
are dissolved or dispersed in an organic solvent, emulsifying the
solution or dispersion by such a way as adding water, and
separating and classifying the obtained particles. The volume
average particle diameter of the toner is preferably in a range
from 3 to 15 .mu.m.
The toner composition of the invention may be mixed with carrier
particles of iron powder, glass beads, nickel powder, ferrite,
magnetite or ferrite surface-coated with a resin (e.g. acrylic
resin and silicone resin) if necessary, to be used as a developer
for an electric latent image. The weight ratio of the toner and
carrier particles is generally 1/99 to 100/0. An electric latent
image can also be formed by bringing into friction with a charging
blade in place of the carrier particles.
The toner composition of the invention is fixed on a support (e.g.
paper and a polyester film) by a copying machine or a printer to be
a recording material. A method for fixing on the support may be
conventionally known heat roll fixing method and flash fixing
method.
Use of the toner composition of the invention makes it easy to
carry out fixing in a temperature difference range as wide as
95.degree. C. or higher (particularly 100.degree. C. or higher)
between a hot offset occurrence temperature and the minimum fixing
temperature at the time of fixing an un-fixed image by a fixing
apparatus.
The non-magnetic single component toner of the sixth invention
contains at least the polyester resin (A) [the polyester resin
(A1), (A2), or (A3) of the first to third inventions] and a
colorant.
With respect to the polyester resin (A) of the sixth invention,
those having a softening point (sp) and a glass transition
temperature (Tg), the point (Tg, sp) being within an area
surrounded by straight lines defined by the following equations (1)
to (4) [the inside of the parallelogram of FIG. 1], preferably
within an area defined by the following (1), (2), (3'), and (4'),
and more preferably within an area defined by the following (1'),
(2'), (3''), and (4') can be used: sp=4Tg-110, equation (1):
sp=4Tg-170, equation (2): sp=90, equation (3): sp=130, equation
(4): sp=4Tg-114, equation (1'): sp=4Tg-166, equation (2'): sp=93,
equation (3'): sp=95, and equation (3''): sp=127. equation (4):
That is, the sp of the polyester resin (A) is within a range from
90 to 130.degree. C. The lower limit is preferably 93.degree. C.
and more preferably 95.degree. C. and the upper limit is preferably
127.degree. C. The Tg is preferably in a range from 50 to
65.degree. C. and more preferably in a range from 51 to 64.degree.
C. if sp is 90.degree. C. and preferably in a range from 60 to
75.degree. C. and more preferably in a range from 61 to 74.degree.
C. if sp is 130.degree. C.
In this case, if the sp is lower than the above-mentioned range, an
offset phenomenon may possibly occurs at the time of fixing and if
it is higher than the above-mentioned range, the fixing energy is
increased and the luster and transparency tend to be deteriorated
in the case of a color toner. If the Tg is lower than the
above-mentioned range, agglomerates and cohesion of the toner may
possibly be caused and if the Tg is higher than the above-mentioned
range, the fixing strength at the time of heat fixing tends to be
lowered, so that the sp and Tg are preferably to be within the
above-mentioned ranges. The sp may be adjusted mainly by the
molecular weight of the resin and it is preferable to adjust Mn
preferably within a range from 2000 to 20000 and more preferably
within a range from 3000 to 12000. The Tg may be adjusted by
selecting the monomer components composing the resin and
practically the Tg is increased by using an aromatic polycarboxylic
acid as a main component for the polycarboxylic acid component.
The sp of the polyester resin (A) is measured by a flow tester
described in JIS K7210 and K6719, as opposed to the softening point
in the above-mentioned second invention. Practically, measurement
is carried out using a flow tester (CFT-500 manufactured by
Shimadzu Corp.) by applying a load of 30 kg/cm.sup.2 by a plunger
with a surface area of 1 cm.sup.2 while heating about 1 g of a
sample at a heating speed of 3.degree. C./min.; extruding the
sample out of a die with a hole diameter of 1 mm and a length of 10
mm. Accordingly, a plunger stroke-temperature curve is drawn and in
the case the height of the S-shape curve is denoted by h, the
temperature corresponding to h/2 is defined as the softening
point.
Two kinds of resins may be used in combination for the polyester
resin (A) and to satisfy all of the low temperature fixing
property, hot offset resistance, and grindability, it is preferable
that the resin (A) comprises the above-mentioned linear polyester
resin (Aa) and non-linear polyester resin s (Ab). The resins (Aa)
and (Ab) may comprise two or more resins, respectively.
The weight ratio of (Aa) and (Ab) is preferably 10/90 to 80/20,
more preferably 20/80 to 75/25, and even more preferably 25/75 to
70/30.
The polyester resin to be used in the sixth invention preferably
comprises the resin (A) alone, however another polyester resin may
be added to an extent that the properties of the polyester resin
are not deteriorated. Another resin may be polyester resins other
than the resin (A) and having Mn in a range from 1000 to 1,000,000.
The content of another resin is preferably 10% or less and more
preferably 5% or less.
In the case the resin (A) is used in combination with another
resin, it is preferable that the entire body of the polyester resin
for a toner of the invention keeps the physical properties
(molecular weight, Tg, and THF-insoluble fraction) within the
above-mentioned ranges.
Examples of a colorant to be used for the non-magnetic toner of the
invention may be same as described above-mentioned.
The non-magnetic toner of the invention comprises fine particles of
at least one kind of finely granular additive (a fluidizing agent)
on the surface of the toner particles. They are added mainly for
improving the agglomeration, cohesion, and fluidity of the toner
particles and also improving the friction electrostatic property
and durability as a toner. Practically, organic and inorganic fine
particles having an average primary particle diameter in a range
from 0.001 to 5 .mu.m, preferably 0.002 to 3 .mu.m, and which may
optionally be surface-treated are usable and examples are particles
of fluoro resins such as poly(vinylidene fluoride) and
polytetrafluoroethylene; fatty acid metal salts such as zinc
stearate and calcium stearate; resin beads containing mainly
poly(methyl methacrylate) and silicone resin; minerals such as talc
and hydrotalcite; and metal oxides such as silicon oxide (colloidal
silica or the like), aluminum oxide, titanium oxide, zinc oxide,
and tin oxide.
The non-magnetic toner of the invention may contain, if necessary,
one or more kinds of the above-mentioned commonly used additives
such as a release agent and a charge control agent.
With respect to the component ratios of the non-magnetic toner of
the invention, based on the toner weight, the ratio of the
polyester resin (A) of the invention is preferably in a range from
30 to 97%, more preferably from 40 to 95%, and even more preferably
from 45 to 92%; the ratio of the colorant is preferably in a range
from 0.05 to 60%, more preferably from 0.1 to 55%, and even more
preferably from 0.5 to 50%; and with respect to the additives, the
ratio of the finely granular additive is preferably in a range from
0.01 to 10%, more preferably from 0.05 to 5%, and even more
preferably from 0.1 to 4%; the ratio of the release agent is
preferably in a range from 0 to 30%, more preferably from 0.5 to
20%, and even more preferably from 1 to 10%; the ratio of the
charge control agent is preferably in a range from 0 to 20%, more
preferably from 0.1 to 10%, and even more preferably from 0.5 to
7.5%; and the total content of these additives (including the
finely granular additive) is preferably in a range from 3 to 70%,
more preferably from 4 to 58%, and even more preferably from 5 to
50%. If the component ratios of the toner are within the
above-mentioned ranges, it becomes easy to obtain a toner with
excellent electrostatic property.
The toner composition of the invention may be obtained by any
conventionally known method such as a kneading and grinding method,
an emulsifying phase-inversion method, and a polymerizing
method.
The non-magnetic toner of the invention is fixed on a support (e.g.
paper and a polyester film) by a copying machine or a printer to be
a recording material. A method for fixing on the support may be
conventionally known heat roll fixing method and flash fixing
method.
Next, the resin (K) for resin particles of the seventh invention
comprises a polyester resin (K1) obtained by polycondensing one or
more kinds of polyol components and one or more kinds of
polycarboxylic acid components. The resin (K1) contains an
aliphatic diol having 2 to 6 carbon atoms as an indispensable
component.
The aliphatic diol having 2 to 6 carbon atoms may include those
exemplified above and two or more kinds may be used in combination.
Preferable examples are ethylene glycol, 1,2-propylene glycol, and
neopentyl glycol preferable; more preferably ethylene glycol and
1,2-propylene glycol; and even more preferable 1,2-propylene
glycol.
The content of the aliphatic diol having 2 to 6 carbon atoms in the
polyol component in the resin (K1) is generally in a range from 85
to 100% by mole, preferably in a range from 90 to 100% by mole,
more preferably in a range from 95 to 100% by mole, and even more
preferably 100%. If the content of the aliphatic diol having 2 to 6
carbon atoms is 85% by mole or higher, the strength of the resin
itself is increased and the low temperature fixing property is
improved. However, in the case 1,2-propylene glycol is used for the
aliphatic diol having 2 to 6 carbon atoms, the content is generally
in a range from 70 to 100% by mole, preferably from 75 to 100% by
mole, more preferably from 90 to 100% by mole, furthermore
preferably from 95 to 100% by mole, and even more preferably 100%.
If the content of 1,2-propylene glycol is 70% by mole or higher,
the strength of the resin itself is increased and the low
temperature fixing property is improved.
The polyol component may contain 15% by mole or less of polyhydric
alcohols (30% by mole or less in the case of using 1,2-propylene
glycol) other than the aliphatic diol having 2 to 6 carbon
atoms.
Examples of a dihydric alcohol (diol) among the polyhydric alcohols
may include, as described above, aliphatic diol having 7 to 36
carbon atoms; polyalkylene ether glycol having 4 to 36 carbon
atoms; adducts of AO having 2 to 4 carbon atoms to aliphatic diols
having 2 to 6 and 7 to 36 carbon atoms; alicyclic diols having 6 to
36 carbon atoms; adducts of AO having 2 to 4 carbon atoms to
alicyclic diols; and adducts of AO having 2 to 4 carbon atoms to
bisphenols.
Examples of tri- to octa-hydric or higher hydric alcohols among the
polyhydric alcohol are those exemplified above.
Among these polyhydric alcohols are preferably polyalkylene ether
glycol having 4 to 36 carbon atoms; alicyclic diols; adducts of AO
having 2 to 4 carbon atoms to alicyclic diols having 4 to 36 carbon
atoms; adducts of AO having 2 to 4 carbon atoms to bisphenols; and
adducts of AO having 2 to 4 carbon atoms to novolak resins; and
more preferably adducts of AO (EO and PO) having 2 to 4 carbon
atoms to bisphenols and adducts of AO (EO and PO) having 2 to 4
carbon atoms to novolak resins.
Examples of the polycarboxylic acid components are those same as
exemplified above.
Preferable examples among the polycarboxylic acid components are
alkanedicarboxylic acids having 2 to 50 carbon atoms;
alkenedicarboxylic acids having 4 to 50 carbon atoms; aromatic
dicarboxylic acids having 8 to 20 carbon atoms; and aromatic
polycarboxylic acids having 9 to 20 carbon atoms: more preferable
examples are adipic acid, alkenylsuccinic acid having 16 to 50
carbon atoms, terephthalic acid, isophthalic acid, maleic acid,
fumaric acid, trimellitic acid, pyromellitic acid, and combinations
of these acids: and even more preferable examples are adipic acid,
terephthalic acid, trimellitic acid, and combinations of these
acids. Anhydrides and lower alkyl esters of these acids are also
preferable.
Further, the polycarboxylic acid components are also preferable to
comprise an aromatic polycarboxylic acid (di- to hexa- or higher)
and an aliphatic polycarboxylic acid (di- to hexa- or higher) and
contain 60% by mole or more of the aromatic polycarboxylic acid.
The lower limit of the content of the aromatic polycarboxylic acid
is more preferably 70% by mole and furthermore preferably 80% by
mole and the upper limit is more preferably 99% by mole and
furthermore preferably 98% by mole. If the content of the aromatic
polycarboxylic acid is 60% by mole, the resin strength is increased
and the low temperature fixing property is further improved.
The polyester resin (K1) in the invention can be produced by the
same manner as a common polyester production method. Examples of
the method are those exemplified above.
Mn of the THF-soluble fraction of the resin (K1) is 1000 to 9500.
The lower limit is preferably 1200 and more preferably 1400 and the
upper limit is preferably 9300 and more preferably 9100. If Mn is
1000 or higher, the resin strength is good and if it is 9500 or
lower, the low temperature fixing property is good.
Mp of the THF-soluble fraction of the resin (K1) is preferably 1200
to 250000 in terms of the balance between the resin strength and
low temperature fixing property. The lower limit is more preferably
1500 and the upper limit is more preferably 23000.
The content of the components with 500 or less molecular weight in
a chromatogram by gel permeation chromatography of the THF-soluble
components of the resin (K1) is preferably 3% or lower and more
preferably 2.5% or lower. If the content of the components with 500
or less molecular weight is 3% or lower, in the case of using the
resin for a toner, the fluidity is improved and the image stability
is improved at the time of continuous printing. In the case two or
more kinds of resins are used as the resin (K1), even if a resin
having a high content of components with 500 or less molecular
weight is contained, it is allowed if the content in the entire
resin (K1) is within the above-mentioned range.
Tg of the resin (K1) is preferably in a range from 40 to 90.degree.
C., more preferably from 45 to 85.degree. C., and even more
preferably from 50 to 80.degree. C. in terms of the thermal storage
property and low temperature fixing property.
The THF-insoluble fraction in the resin (K1) is preferably in a
content of 70% or less in terms of low temperature fixing property.
The lower limit is more preferably 1% and even more preferably 3%
and the upper limit is more preferably 40% and even more preferably
30%.
Hydroxy value (mgKOH/g) of the resin (K1) is preferably 70 or
lower, more preferably in a range from 5 to 40, and even more
preferably in a range from 10 to 30. If the hydroxyl value is 70 or
lower, the environment stability and the amount of electrostatic
charge are improved. Acid value (mgKOH/g) of the resin (K1) is
preferably 40 or lower, more preferably in a range from 1 to 30,
and even more preferably in a range from 2 to 25, most preferably
in a range from 5 to 20. If the acid value is 40 or lower, the
environment stability is improved. If the resin has a proper acid
value, the rising up of charging is improved and thus it is
preferable.
Two or more kinds of resins may be used in combination for the
polyester resin (K1) and in terms of attainment of both
satisfactory low temperature fixing property and hot offset
resistance, the resin (K1) is preferable to comprise a linear
polyester resin (K1a) and a non-linear polyester resin (K1b) Two or
more kinds of the resins for each (K1a) and (K1b) may be used.
The weight ratio of the resins (K1a) and (K1b) is preferably in a
range from 10/90 to 80/20, more preferably from 20/80 to 75/25, and
even more preferably from 25/75 to 70/30.
Also, because of the same reason, Mn of the THF-soluble fraction of
the resin (K1b) is preferable to be higher than Mn of the resin
(K1a) by at least 200 and more preferable by at least 300.
The linear polyester resin (K1a) is generally obtained by
polycondensing the above-mentioned diol and dicarboxylic acid. It
may be modified in the molecule terminals with an anhydride of the
above-mentioned polycarboxylic acids (including tri- or higher
valent polycarboxylic acids).
A non-linear polyester resin (K1b) is generally obtained by
reaction of the above-mentioned diol and dicarboxylic acid as well
as the above-mentioned tri- or higher valent polycarboxylic acids
and/or tri- or higher hydric polyalcohols. Examples of the tri- or
higher valent polycarboxylic acids and/or tri- or higher hydric
polyalcohols are preferably adducts (average addition molar number
2 to 30) of AO having 2 to 4 carbon atoms to novolak resins and
tri- to hexa- or higher aromatic polycarboxylic acids having 9 to
20 carbon atoms (e.g. trimellitic acid and pyromellitic acid) and
more preferably tri- to hexa- or higher aromatic polycarboxylic
acids.
With respect to the ratio of the tri- or higher valent
polycarboxylic acids and tri- or higher hydric polyalcohols in the
case of obtaining the resin (K1b), the total of the moles of them
in the total moles of the polyol components and the polycarboxylic
acid components is preferably in a range from 0.1 to 40% by mole,
more preferably in a range from 1 to 25% by mole, and even more
preferably in a range from 3 to 20% by mole.
The polyester resin (K1) is preferably the polyester resin (A1) of
the first invention and/or the polyester resin (A2) of the second
invention.
The THF-insoluble fraction of the resin (K1a) is preferably 3% or
less, more preferably 1% or less, and even more preferably 0%. As
the THF-insoluble fraction of the resin (K1a) is less, it is more
preferable in terms of the low temperature fixing property.
The THF-insoluble fraction of the resin (K1b) is preferably 1 to
70%. The lower limit is more preferably 2% and even more preferably
5% and an upper limit is more preferably 60% and even more
preferably 50%. Including the THF-insoluble fraction within the
above-mentioned range is preferable in terms of the improvement of
the hot offset resistance.
The resin (K) in the resin particles of the invention may contain
one or more kinds of other resins (K2) to an extent that the
properties of the polyester resin (K1) are not deteriorated.
Examples of other resins are polyester resin other then the resin
(K1), vinyl resin, polyurethane resin, epoxy resin, polyester
resin, polyamide resin, polyimide resin, silicon type resin, phenol
resin, melamine resin, urea resin, aniline resin, ionomer resin,
and polycarbonate resin and preferable examples among them are
vinyl resin, polyurethane resin, epoxy resin, polyester resin, and
combinations of these resins. Practical examples of vinyl resin,
polyurethane resin, epoxy resin, and polyester resin are those
described in International publication WO 03/106541.
Mn of the resin (K2) is preferably in a range from 500 to 2,000,000
and more preferably from 1000 to 1,000,000. The content of the
resin (K2) in the resin (K) is preferably 10% or less and more
preferably 0.1 to 8%.
In the case another resin (K2) is added to the resin (K), it is
preferable for the resin (K) as a whole have the above-mentioned
preferable physical properties of the resin (K1) (molecular weight,
Tg, and THF-soluble fraction) within the above-mentioned
ranges.
The resin particles of the invention may contain, together with the
resin (K), one or more kinds of additives such as a colorant, a
release agent, a charge control agent, and a fluidizing agent. In
the case the resin particles are used for a powder coating, an
electrophotographic toner, an electrostatic recording toner, or an
electrostatic printing toner, the colorant is added
indispensably.
As the colorant are any dye and pigment used as the colorant for a
toner usable. Practical examples are those exemplified above and
they may be used alone or two or more kinds of them may be used in
form of a mixture. Further, if necessary, a magnetic powder (a
powder of a ferromagnetic metal such as iron, cobalt, and nickel or
a compound such as magnetite, hematite, and ferrite) may be added
for a function as a colorant. The content of the colorant is
preferably in a range from 1 to 40 part and more preferably in a
range from 3 to 10 part to 100 part of the resin (K) of the resin
particles of the invention. In the case of using the magnetic
powder, it is preferably in a range from 20 to 150 part and more
preferably in a range from 40 to 120 part.
Examples of the release agent, charge control agent, and fluidizing
agent are those exemplified above.
With respect to the component ratios of the resin particles of the
invention, based on the weight of the composition, the ratio of the
resin (K) of is preferably in a range from 30 to 97%, more
preferably from 40 to 95%, and more preferably from 45 to 92%; with
respect to the additives, the ratio of the colorant is preferably
in a range from 0.05 to 60%, more preferably from 0.1 to 55%, and
even more preferably from 0.5 to 50%; the ratio of the release
agent is preferably in a range from 0 to 30%, more preferably from
0.5 to 20%, and even more preferably from 1 to 10%; the ratio of
the charge control agent is preferably in a range from 0 to 20%,
more preferably from 0.1 to 10%, and even more preferably from 0.5
to 7.5%; and the ratio of the fluidizing agent is preferably in a
range from 0 to 10%, more preferably from 0 to 5%, and even more
preferably from 0.1 to 4%. Also, the total content of these
additives is preferably in a range from 3 to 70%, more preferably
from 5 to 60%, even more preferably from 8 to 55%. If the component
ratios are within the above-mentioned ranges, it becomes easy to
obtain a toner with excellent electrostatic property.
The resin particles of the invention are obtained by dissolving or
dispersing components including the resin (K) in an organic solvent
for producing an oil-based mixed solution (I), converting it to a
water-based dispersion with a water-based medium (II), and removing
the solvents such as the organic solvent and water from the
water-based dispersion.
The volume average particle diameter of the resin particles is
preferably 2 to 20 .mu.m. The lower limit is more preferably 3
.mu.m and even more preferably 4 .mu.m and the upper limit is more
preferably 15 .mu.m and even more preferably 12 .mu.m.
The volume average particle diameter (D50) is measured by laser
type particle diameter distribution measurement apparatus [e.g.
trade name: LA-920 (manufactured by Horiba Seisakusho) and trade
name: Multisizer III (manufactured by Coulter Co.)].
The water-based medium (II) may contain an emulsifier and a
dispersant for making formation of oil droplets of the oil-based
mixed solution (I) easy in a water-based dispersion and keeping the
formed oil droplets stably. Examples of the emulsifier and
dispersant to be used may be conventionally known surfactant (S),
fine particles (M), water-soluble polymer (T). A solvent (U) and a
plasticizer (V) may be used as assisting agents for the emulsifier
and dispersant in combination.
As the surfactant (S) are a wide range of conventionally known ones
usable and examples are an anionic surfactant (S-1), a cationic
surfactant (S-2), an amphoteric surfactant (S-3), and a nonionic
surfactant (S-4). Tow or more kinds of surfactants may be used as
the surfactant (S).
Examples of the anionic surfactant (S-1) include carboxylic acid
and its salts; sulfuric acid ester salts, salts of carboxymethyl
compounds, sulfonic acid salts, and phosphoric acid ester
salts.
Examples of the cationic surfactant (S-2) include quaternary
ammonium salt type surfactants and amine salts type
surfactants.
Examples of the amphoteric surfactant (S-3) include carboxylic acid
salt type amphoteric surfactants; sulfuric acid ester salt type
amphoteric surfactant, sulfonic acid salt type amphoteric
surfactants, and phosphoric acid ester salt type amphoteric
surfactant.
Examples of the nonionic surfactant (S-4) include AO-adduct type
nonionic surfactants and polyhydric alcohol type nonionic
surfactants.
Practical examples of these surfactants are those described in
International publication WO 03/106541.
The content of the surfactant (S) in the water-based medium (II) is
preferably in a range from 0.01 to 30% and more preferably from 0.1
to 20%.
The fine particles (M) are not particularly limited if they are
resin particles suitable for forming a water-based dispersion and
may be fine particles of thermoplastic resins and fine particles of
thermosetting resins and examples are fine particles of vinyl
resin, polyurethane resin, epoxy resin, polyester resin, polyamide
resin, polyimide resin, silicon type resin, phenol resin, melamine
resin, urea resin, aniline resin, ionomer resin, and polycarbonate
resin and two or more kinds of the resins may be used in
combination. Preferable examples among the mare resin particles of
vinyl resin, polyurethane resin, epoxy resin, polyester resin, and
combinations of these resins, from a viewpoint of the easiness of
obtaining the water-based dispersion of finely spherical resin
particles. Practical examples of these resins are those described
in International publication WO 03/106541.
The volume average particle diameter of the particles (M) is
preferably in a range from 20 to 500 nm and more preferably in a
range from 25 to 300 nm.
The content of the fine particles (M) in the water-based medium
(II) is preferably in a range from 0.01 to 30% and more preferably
in a range from 0.1 to 20%.
Examples of the water-soluble polymer (T) are cellulose type
compounds (e.g. methyl cellulose, ethyl cellulose, hydroxyethyl
cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose,
hydroxypropyl cellulose, and their saponified compounds); gelatin,
starch, dextrin, gum arabi, chitin, chitosan, polyvinyl alcohol,
polyvinylpyrrolidone, polyethylene glycol, polyethylene imine,
polyacrylamide, polymer containing acrylic acid (salts) (e.g.
poly(sodium acrylate), poly (potassium acrylate), poly(ammonium
acrylate), poly(acrylic acid) partially neutralized with sodium
hydroxide, and sodium acrylate-acrylic acid ester copolymer),
styrene-maleic anhydride copolymer (partially) neutralized with
sodium hydroxide, and water-soluble polyurethane (e.g. reaction
products of polyisocyanate with polyethylene glycol or
polycaprolactone diol).
The weight average molecular weight of these water-soluble polymers
(T) is preferably in a range from 1,000 to 10,000,000.
The content of the water-soluble polymer (T) in water-based medium
(II) is preferably in a range from 0.01 to 20% and more preferably
from 0.1 to 10%.
Examples of the solvent (U) to be used in the invention may include
aromatic hydrocarbon type solvents such as toluene, xylene,
ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon type
solvents such as n-hexane, n-heptane, mineral spirit, and
cyclohexane; halogen type solvents such as methyl chloride, methyl
bromide, methyl iodide, methylene dichloride, carbon tetrachloride,
trichloroethylene, and perchloroethylene; ester or ester ether type
solvents such as ethyl acetate, butyl acetate, methoxybutyl
acetate, methylcellosolve, and ethylcellosolve; ether type solvents
such as diethyl ether, tetrahydrofuran, dioxane, ethylcellosolve,
butylcellosolve, and propylene glycol monomethyl ether; ketone type
solvents such as acetone, methyl ethyl ketone, methyl isobutyl
ketone, di-n-butyl ketone, and cyclohexanone; alcohol type solvents
such as methanol, ethanol, n-propanol, isopropanol, n-butanol,
isobutanol, tert-butanol, 2-ethylhexyl alcohol, and benzyl alcohol;
amide type solvents such as dimethylformamide and
dimethylacetamide; sulfoxide type solvents such as dimethyl
sulfoxide; heterocyclic compound type solvents such as
N-methylpyrrolidone; and mixed solvents of two or more kinds of
these solvents.
The content of the solvent (U) in the water-based medium (II) is
preferably in a range from 0.01 to 50% and more preferably from 0.1
to 30%.
The plasticizer (V) is not particularly limited and the following
can be exemplified: (V1) phthalic acid esters having 8 to 60 carbon
atoms [e.g. dibutyl phthalate, dioctyl phthalate, butyl benzyl
phthalate, and diisodecyl phthalate]; (V2) aliphatic dibasic acid
esters having 6 to 60 carbon atoms [e.g. 2-ethylhexyl adipate and
2-ethylhexyl sebacate]; (V3) trimellitic acid esters having 10 to
70 carbon atoms [e.g. 2-ethylhexyl trimellitate and trioctyl
trimellitate]; (V4) phosphoric acid esters having 8 to 60 carbon
atoms [e.g. triethyl phosphate, tri-2-ethylhexyl phosphate, and
tricresyl phosphate]; (V5) fatty acid esters having 8 to 50 carbon
atoms [e.g. butyl oleate]; and (V6) mixtures of two or more kinds
of these compounds.
The content of the plasticizer (V) in the water-based medium (II)
is preferably in a range from 0.01 to 10% and more preferably from
0.1 to 8%.
In the invention, at the time of obtaining the water-based
dispersion from the oil-based mixed solution (I) and the
water-based medium (II), the mixing ratio is preferably 50 to 500
part and more preferably 80 to 300 part of the water-based medium
(II) to 100 part of the oil-based mixed solution (I). The mixing
order is not particularly limited and (II) may be added to (I),
contrarily, (I) may be added to (II), or they may be added
simultaneously. The mixing may be carried out under stirring or
dispersing condition or stirring and dispersing treatment may be
carried out after mixing them.
To obtain the water-based dispersion from the oil-based mixed
solution (I) and the water-based medium (II), a dispersion
apparatus may be used. The dispersion apparatus to be used is not
particularly limited if it is commonly commercialized emulsifiers
and dispersion apparatuses, and examples of the apparatus include
batch emulsifiers such as a homogenizer (manufactured by IKA Japan
K.K.), Polytron (manufactured by Kinematica), and TK Auto Homomixer
(manufactured by Tokushu Kika Kogyo Co., Ltd.), continuous
emulsifiers such as Ebara Milder (manufactured by Ebara
Corporation), TK Fillmix and TK Pipe Line Homomixer (manufactured
by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (manufactured by
Shinko Pantech Co., Ltd.), a slasher and Trigonal wet pulverizer
(manufactured by Mitsui Miike Machinery Co., Ltd.), Cabitron
(manufactured by Eurotech, Ltd.), and Fine Flow Mill (manufactured
by Pacific Machinery & Engineering Co., Ltd.), high-pressure
emulsifiers such as Microfluidizer (manufactured by Mizuho Kogyo
Co., Ltd.), Nanomizer (manufactured by Nanomizer), and APV Gaulin
(manufactured by Gaulin) membrane emulsifiers such as a membrane
emulsifier (manufactured by REICA), vibration emulsifiers such as
Vibro Mixer (manufactured by REICA), and ultrasonic emulsifiers
such as an ultrasonic homogenizer (manufactured by BRANSON).
Preferable apparatus among them in terms of evenness of the
particle diameter are APV Gaulin, homogenizer, TK Auto-homomixer,
Ebara Milder, TK Filmix, and TK Pipeline Homomixer.
After the water-based dispersion containing resin particles is
obtained from the water-based dispersion containing the resin (K)
obtained by the above-mentioned production method, if necessary by
removing the organic solvent, the obtained water-based dispersion
is subjected to solid-liquid separation (if necessary, solid-liquid
separation is repeated by adding water or the like) and the
separated solid is dried for removing the solvents such as organic
solvent and water to obtain the resin particles of the
invention.
The method for removing the solvents may be the following methods
[1] to [3] and combinations of them: [1] a method for drying out
the water-based dispersion under reduced pressure or normal
pressure; [2] a method for solid-liquid separation by a centrifugal
separator, Supakura Filter, and/or filter press and drying of the
obtained solid; and [3] a method of freezing the water-based
dispersion and drying the frozen dispersion (so-called
freeze-drying method).
In the invention of the above-mentioned [1] and [2], commonly known
facilities such as a fluidized bed type drying apparatus, a vacuum
drying apparatus, and an air circulation drying apparatus may be
used as a drying apparatus.
If necessary, an air blowing classification apparatus or sieve may
be used for classification to obtain desired particle size
distribution.
The remaining solvent amount in the resin particles of the
invention after the solvent removal is preferably 200 ppm or less
for the organic solvent and 0.5% or lower for water.
In the case of using the resin particles of the seventh invention
for a toner, based on the necessity, being mixed with iron powder,
glass beads, nickel powder, ferrite, magnetite or ferrite
surface-coated with a resin (e.g. acrylic resin and silicone
resin), the resin particles are used as a developer for an electric
latent image. The weight ratio of the toner and carrier particles
is generally 1/99 to 100/0. An electric latent image can also be
formed by bringing into friction with a member such as a charging
blade in place of the carrier particles.
In the case of using the resin particles of the seventh invention
for a toner, the toner is fixed on a support (e.g. paper and a
polyester film) by a copying machine or a printer to be a recording
material. A method for fixing on the support may be conventionally
known heat roll fixing method and flash fixing method.
The composite resin particles of the eighth invention comprises
resin particles (P) to be a core and resin fine particles (Q)
adhering to the surfaces of the particles (P) and the resin
particles (P) contain a resin (p).
The resin (p) comprises a specified polyester resin (p1) obtained
by polycondensing at least one kind polyol component and at least
one kind polycarboxylic acid component and/or a resin (p2)
containing the resin (p1) as a component unit. The resins (p1) and
(p2) may include two or more kinds of resins, respectively.
Examples of the resin (p1) may be those same as exemplified for the
polyester resin (K1).
In terms of the thermal storage property, low temperature melting
property and low temperature fixing property, Tg of the resin (p1)
is preferably in a range from 30 to 120.degree. C., more preferably
from 35 to 100.degree. C., and even more preferably from 40 to
90.degree. C.
Hydroxy value (mgKOH/g) of the resin (p1) is preferably 70 or
lower, more preferably in a range from 5 to 50, and even more
preferably in a range from 10 to 40. If the hydroxyl value is 70 or
lower, the environment stability and the amount of electrostatic
charge in the case of using it for a toner are improved. Acid value
(mgKOH/g) of the resin (p1) is preferably 45 or lower, more
preferably in a range from 1 to 40, furthermore more preferably in
a range from 2 to 35, and even more preferably in a range from 5 to
30. If the acid value is 45 or lower, the environment stability is
improved. If the resin has a proper acid value, the rising up of
charging is improved and thus it is preferable.
The polyester resin (p1) is preferable to be the polyester resin
(A1) of the first invention and/or the polyester resin (A2) of the
second invention.
The resin (p) contained in the resin particles (P) of the invention
may be a resin (p2) comprising the above-mentioned polyester resin
(p1) as a component unit of a polymer skeleton and the resins (p1)
and (p2) may be used in combination.
The resin (p2) may be polyurethane resin comprising the resin (p1)
and polyisocyanate (15) described below; epoxy resin comprising the
resin (p1) and polyepoxide (18) described below; and polyamide
resin comprising the resin (p1) and polyamine (16) described
below.
Among them are the polyurethane resin and epoxy resin preferable
and the polyurethane resin more preferable.
Between the resins (p1) and (p2) is the resin (p2) preferable since
the low temperature melting property and low temperature fixing
property become more preferable.
The resin (p2) may be obtained by reaction of a precursor (p0)
containing the polyester resin (p1) as a component unit in a
molecule and a curing agent or by reaction of a combination of a
reactive group-containing prepolymer (.alpha.) containing the
polyester resin (p1) as a component unit and a curing agent
(.beta.)
The combination of a reactive group contained in a reactive
group-containing prepolymer (.alpha.) and a curing agent (.beta.)
may be the following combinations [1] and [2]: combination [1]:
combination of a reactive group-containing prepolymer (.alpha.1)
containing a functional group capable of reacting on an active
hydrogen-containing group and an active hydrogen-containing
compound (.beta.1); and combination [2]: combination of a reactive
group-containing prepolymer (.alpha.2) containing an active
hydrogen-containing group and a curing agent (.beta.2) having a
functional group capable of reacting on an active
hydrogen-containing group.
Examples of a functional group capable of reacting with an active
hydrogen-containing group include an isocyanate group, a blocked
isosyanate group, an epoxy group, an acid anhydride group, and an
acid halide (e.g., acid chlorides and acid bromides) group.
Among them, an isocyanate group, a blocked isocyanate group, and an
epoxy group are preferably used, more preferably an isocyanate
group and a blocked isocyanate group.
In this regard, it is to be noted that the blocked isocyanate group
means an isocyanate group that is blocked with a blocking
agent.
Examples of the blocking agent include well-known blocking agents
such as oximes (e.g., acetoxime, methyl isobutyl ketoxime, diethyl
ketoxime, cyclopentanone oxime, cyclohexanone oxime and methyl
ethyl ketoxime), lactams (e.g., .gamma.-butyrolactam,
.epsilon.-caprolactam, and .gamma.-valerolactam), aliphatic
alcohols having 1 to 20 carbon atoms (e.g., ethanol, methanol, and
octanol), phenols (e.g., phenol, m-cresol, xylenol, and
nonylphenol), activemethylene compounds (e.g., acetylacetone, ethyl
malonate, and ethyl acetoacetate), basic nitrogen-containing
compounds (e.g., N,N-diethylhydroxylamine, 2-hydroxypiridine,
pyridine N-oxide, and 2-mercaptopyridine), and mixtures of two or
more of them.
Among these blocking agents, oximes are preferably used, more
preferably methyl ethyl ketoxime.
A method for introducing the reactive group into the polyester
resin (p1) is not particularly limited and for example, a method of
reacting a compound containing a functional group (reactive group)
capable of reacting on the functional group remaining in the
polyester resin (p1) can be employed.
According to this method, reaction of polyisocyanate on the
polyester resin (p1) is caused to obtain an isocyanate
group-containing prepolymer: reaction of block polyisocyanate is
caused to obtain block isocyanate group-containing prepolymer:
reaction of polyepoxide is caused to obtain epoxy group-containing
prepolymer: and reaction of a compound having two or more of acid
anhydride groups is caused to obtain acid anhydride
group-containing prepolymer.
On the basis of mole ratio [NCO]/[OH] of the isocyanate group [NCO]
and hydroxyl group [OH], the ratio of the polyester resin (p1) and
the polyisocyanate is preferably in a range from 5/1 to 1/1, more
preferably from 4/1 to 1.2/1; and even more preferably from 2.5/1
to 1.5/1. That is, the upper limit of the mole ratio [NCO]/[OH] in
this case is preferably 5/1, more preferably 4/1, and even more
preferably 2.5/1 and similarly the lower limit is preferably 1/1,
more preferably 1.2/1, and even more preferably 1.5/1.
The preferable ratio is same also in the case of other prepolymers
with simple change of the components.
The average number of the reactive groups contained in the reactive
group-containing prepolymer (.alpha.) per one molecule is
preferable 1 to 3, more preferably 1.5 to 3, and even more
preferably 1.8 to 2.5. If it is within the range, the resin (q) to
be obtained by reaction with the curing agent (.beta.) tends to
have a high mechanical strength.
Mn of the reactive group-containing prepolymer (.alpha.) is
preferably in a range from 1,000 to 30,000, more preferably from
1,500 to 20,000, and even more preferably 2,000 to 10,000.
Mw of the reactive group-containing prepolymer (.alpha.) is
preferably in a range from 1,500 to 50,000, more preferably from
2,000 to 40,000, and even more preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (.alpha.)
is preferably in a range from 50 to 50,000 MPaS, more preferably
from 100 to 5,000 MPaS, and even more preferably 150 to 3,000 MPaS
at 100.degree. C.
If it is within the range, it tends to be easy to obtain
spindle-shaped composite resin particles in a sharp particle size
distribution even if the amount of the solvent is small.
Examples of the active hydrogen-containing compound (.beta.1) may
include, as described below, water, diols (11), tri- to hexa- or
higher hydric polyols (12), dicarboxylic acids (13), tri- and
tetra- or higher valent polycarboxylic acids (14), polyamines (16),
polythiols (17) and further polyamines optionally blocked with
removable compounds and polyols optionally blocked with removable
compounds.
Examples of a polyamine blocked with a removable compound include
ketimine compounds obtained by dehydration between the polyamines
(16) and ketones having 3 to 8 carbon atoms (e.g., acetone, methyl
ethyl ketone, and methyl isobutyl ketone), aldimine compounds
obtained by dehydration between the polyamines and aldehyde
compounds having 2 to 8 carbon atome (e.g., formaldehyde and
acetaldehyde), enamine compounds obtainable from the polyamines and
ketones having 3 to 8 carbon atoms or aldehydes having 2 to 8
carbon atoms, and oxazolidine compounds.
Among these active hydrogen group-containing compounds (a021),
polyamines which may be blocked, polyols which may be blocked, and
water are preferably used, more preferably polyamines which may be
blocked and water, even more preferably polyamines, ketimine
compounds and water, most preferably 4,4'-diaminodiphenylmethane,
xylylenediamine, isophoronediamine, ethylenediamine,
diethylenetriamine, triethylenetetramine, ketimine compounds
obtainable from these polyamines and ketones, and water.
At the time of producing the resin particles (P) (at the time of
producing composite resin particles), if necessary, a reaction
terminator (.beta.s) may be used in combination with the active
hydrogen-containing compound (.beta.1). Combination use of the
compound (.beta.1) with the reaction terminator (.beta.s) at a
specified ratio makes it easy to adjust the molecular weight of the
resin (q) composing the resin particles (Q).
Examples of such a reaction terminator (.beta.s) include monoamines
having 1 to 40 carbon atoms (e.g., diethylamine, dibutylamine,
butylamine, laurylamine, monoethanolamine, and diethanolamine);
blocked monoamines having 3 to 40 carbon atoms (e.g., ketimine
compounds); monools having 1 to 40 carbon atoms (e.g., methanol,
ethanol, isopropanol, butanol, and phenol); monomercaptans having 2
to 40 carbon atoms (e.g., butylmercaptan and laurylmercaptan);
monoisocyanates having 5 to 40 carbon atoms (e.g., butyl
isocyanate, lauryl isocyanate, and phenyl isocyanate); and
monoepoxides having 2 to 40 carbon atoms (e.g., butyl glycidyl
ether).
In the combination (2) described above (that is, in the combination
of the reactive group-containing prepolymer (a 2) having an active
hydrogen-containing group and the curing agent (.beta.2) having a
functional group capable of reacting with an active
hydrogen-containing group), examples of the active
hydrogen-containing group contained in the reactive
group-containing prepolymer (.alpha.) include an amino group,
hydroxyl groups (an alcoholic hydroxyl group and a phenolic
hydroxyl group), a mercapto group, a carboxyl group, and organic
groups obtained by blocking these groups with removable compounds
(e.g., ketones and aldehydes) (e.g., a ketimine-containing group,
an aldimine-containing group, an oxazolidine-containing group, an
enamine-containing group, an acetal-containing group, a
ketal-containing group, a thioacetal-containing group, and a
thioketal-containing group).
Among these active hydrogen-containing groups, an amino group,
hydroxyl groups, and organic groups obtained by blocking these
groups with removable compounds are preferably used, more
preferably hydroxyl groups.
Examples of the curing agent (.beta.2) having a functional group
capable of reacting with an active hydrogen-containing group
include the polyisocyanates (15), the polyepoxides (18), the
dicarboxylic acids (13), the polycarboxylic acids (14), compounds
having two or more acid anhydride groups, and compounds having two
or more acid halide groups.
Among these curing agents (.beta.2), the polyisocyanates and the
polyepoxides are preferably used, more preferably the
polyisocyanates.
Examples of the compounds having two or more acid anhydride groups
are copolymers of pyromellitic anhydride and maleic acid
anhydride.
Examples of the compounds having two or more acid halide groups are
acid halides (acid chlorides, acid bromides, and acid iodides) of
dicarboxylic acids (13) or polycarboxylic acids (14).
At the time of producing the resin particles (P) (at the time of
producing composite resin particles), if necessary, a reaction
terminator (.beta.s) may be used in combination with the curing
agent (.beta.2) containing a functional group reactive on the
active hydrogen-containing group. Combination use of the curing
agent (.beta.2) with the reaction terminator (.beta.s) at a
specified ratio makes it easy to adjust the molecular weight of the
resin (q) composing the resin particles (Q).
With respect to the use amount of the curing agent (.beta.), the
equivalent ratio [.alpha.]/[.beta.] of the equivalent [.alpha.] of
the reactive group of the reactive group-containing prepolymer
(.alpha.) and the equivalent [.beta.] of the active
hydrogen-containing group of the curing agent (.beta.) is
preferably in a range from 1/2 to 2/1, more preferably from 1.5/1
to 1/1.5; and even more preferably 1.2/1 to 1/1.2. That is, the
upper limit of the ratio [.alpha.]/[.beta.] is preferably 2/1, more
preferably 1.5/1, and even more preferably 1.2/1 and similarly the
lower limit is preferably 1/2, more preferably 1/1.5, and even more
preferably 1/1.2.
In this connection, in the case the curing agent (.beta.) is water,
water is considered to be a compound having divalent active
hydrogen-containing group.
Mw of the resin (p) obtained by the reactive group-containing
prepolymer (.alpha.) and the curing agent (.beta.) is preferably
3,000 or higher, more preferably 3,000 to 10,000,000, and even more
preferably 5,000 to 1,000,000. That is, the upper limit of Mw of
the resin (p) is preferably 10,000,000 and more preferably
1,000,000 and similarly the lower limit is preferably 3,000 and
more preferably 5,000.
The length of time of reaction between the reactive
group-containing prepolymer (.alpha.) and the curing agent (.beta.)
is selected according to reactivity that depends on the combination
of the kind of reactive group contained in the prepolymer (a01) and
the curing agent (.beta.), but is preferably in the range of 10
minutes to 40 hours, more preferably in the range of 30 minutes to
24 hours, even more preferably in the range of 30 minutes to 8
hours.
Further, the temperature of the reaction is preferably in the range
of 0 to 150.degree. C., more preferably in the range of 50 to
120.degree. C.
As necessary, a well-known catalyst can be used. Specifically, in
the case of the reaction between isocyanate and an active
hydrogen-containing compound by way of example, dibutyltin laurate,
dioctyltin laurate or the like can be used.
The resin (p) of the resin particles of the invention may contain
one or more kinds of other resins (p3) besides the resins (p1)
and/or (p2) to an extent that the properties of the resins (p1) and
(p2) are not deteriorated.
Examples of the resins (p3) are, besides the resins (p1) and (p2),
polyester resin, vinyl resin, polyurethane resin, epoxy resin,
polyester resin, polyamide resin, polyimide resin, silicon type
resin, phenol resin, melamine resin, urea resin, aniline resin,
ionomer resin, and polycarbonate resin. Preferable examples among
them are vinyl resin, polyurethane resin, epoxy resin, polyester
resin, and combinations of these resins. Practical examples of
vinyl resin, polyurethane resin, epoxy resin, and polyester resin
are those described in International publication WO 03/106541.
Mn of the resin (p3) is preferably in a range from 500 to 2,000,000
and more preferably from 1000 to 1,000,000. The content of the
resin (p3) in the resin (p) is preferably 80% or less, more
preferably 60% or less, and even more preferably 5 to 40%.
The Mn, melting point, Ts, and SP value of the resin (p) may be
adjusted property in the preferable ranges depending on the
uses.
For example, in the case the composite resin particles of the
invention are used for a resin for slush molding and a powder
coating, Mn of the resin (p) is generally from 1,000 to 500,000,
preferably from 1,500 to 200,000, more preferably from 2000 to
100,000, and even more preferably from 2,500 to 10,000. The melting
point (measured by DSC, hereinafter the melting point is value
measured by DSC) of the resin (p) is generally in a range from 0 to
200.degree. C., preferably from 35 to 150.degree. C., more
preferably from 40 to 120.degree. C., and even more preferably from
45 to 100.degree. C. Tg of the resin (p) is generally in a range
from -60 to 100.degree. C., preferably from -50 to 90.degree. C.,
more preferably from -40 to 80.degree. C., and even more preferably
from -30 to 60.degree. C. The SP value of the resin (p) is
generally in a range from 7 to 18, preferably from 8 to 16, and
more preferably from 9 to 14.
In the case of using them for a toner for electrophotography,
electrostatic recording, and electrostatic printing, Mn of the
resin (p) is generally 1,000 to 5,000,000, preferably from 1,500 to
500,000, more preferably from 2,000 to 100,000, and even more from
preferably 2,500 to 50,000. The melting point of the resin (p) is
generally in a range from 20 to 300.degree. C., preferably from 40
to 250.degree. C., more preferably from 60 to 220.degree. C., and
even more preferably from 80 to 200.degree. C. Tg of the resin (p)
is generally in a range from 20 to 200.degree. C., preferably from
30 to 180.degree. C., more preferably from 35 to 160.degree. C.,
and even more preferably from 40 to 100.degree. C. The SP value of
the resin (p) is generally in a range from 7 to 16, preferably from
8 to 15, and more preferably from 9 to 14.
Based on the necessity, besides of the resin (p), the resin
particles (P) may contain one or more kinds of additives (T) (e.g.
various kinds of additives such as a filler, a colorant, a
plasticizer, a release agent, a charge control agent, an
ultraviolet absorbent, an antioxidant, an antistatic agent, a flame
retardant, an antibacterial agent, and a preserver).
Examples of the filler is silica, alumina, titanium oxide, barium
titanate, magnesium titanate, calcium titanate, strontium titanate,
zinc oxide, tin oxide, silicic sand, clay, mica, wollastonite,
diatomaceous earth, chromium oxide, cerium oxide, chromiumoxide,
ceriumoxide, Bengals, antimonytrioxide, magnesium oxide, zirconium
oxide, barium sulfate, barium carbonate, calcium carbonate, silicon
carbide, and silicon nitride.
Conventionally known dyes and pigments are all usable as the
colorant and for example, the above-mentioned exemplified ones and
those described in International publication WO 03/106541 are also
usable.
The above-mentioned plasticizer (V) is used as the plasticizer.
Waxes and silicone oils with a dynamic viscosity of 30 to 100,000
cSt at 25.degree. C. can be used as the release agent.
Conventionally known waxes are usable as the waxes and examples of
the waxes are polyolefin waxes (e.g. polyethylene wax and
polypropylene wax); long chain hydrocarbons (e.g. paraffin wax and
sasol wax); and carbonyl-containing waxes. Preferable examples
among them are carbonyl-containing waxes. Examples of the
carbonyl-containing waxes are polyalkanoic acid esters (e.g.
carnauba wax, montan wax, trimethylol propane tribehenate,
pentaerythritol tetrabehenate, pentaerythritol diacetate
dibehenate, glycerin tribehenate, and 1,18-octadecanediol
distearate); polyalkanol esters (e.g. tristearyl trimellitate and
distearyl maleate); polyalkanoic acid amides (e.g. ethylenediamine
dibehenylamide); polyalkylamide (e.g. trimellitic acid
tris(stearylamide)); and dialkyl ketones (distearyl ketone).
Preferable examples among the carbonyl-containing waxes are
polyalkanoic acid esters.
Conventionally known charge control agents are all usable and
examples of those exemplified above and those described in
International publication WO 03/106541.
With respect to the component ratios of the resin particles (P) of
the invention, based on the weight of the composition, the ratio of
the resin (p) is preferably in a range from 30 to 97%, more
preferably from 40 to 95%, and even more preferably from 45 to 92%;
and with respect to the additives, the ratio of the colorant is
preferably in a range from 0.05 to 60%, more preferably from 0.1 to
55%, and even more preferably from 0.5 to 50%; the ratio of the
release agent is preferably in a range from 0 to 30%, more
preferably from 0.5 to 20%, and even more preferably from 1 to 10%;
the ratio of the charge control agent is preferably in a range from
0 to 20%, more preferably from 0.1 to 10%, and even more preferably
from 0.5 to 7.5%; the ratio of the fluidizing agent is preferably
in a range from 0 to 10%, more preferably from 0 to 5%, and even
more preferably from 0.1 to 4%. The total content of these
additives is preferably in a range from 3 to 70%, more preferably
from 5 to 60%, and even more preferably from 8 to 55%. If the
component ratios are within the above-mentioned ranges, it becomes
easy to obtain a toner with excellent electrostatic property.
The volume average particle diameter of the resin particles (P) of
the invention can be properly planed depending on the uses of the
composite resin particles of the invention.
In the case of using them for a powder coating, a resin for slush
molding and a hot-melt adhesive, it is generally in a range from 10
to 300 .mu.m, preferably from 50 to 300 .mu.m, more preferably from
50 to 200 .mu.m, and even more preferably from 80 to 180 .mu.m, and
in the case of using them for an electrophotographic toner, an
electrostatic recording toner, and an electrostatic printing toner,
it is generally in a range from 0.1 to 100 .mu.m, preferably from
0.5 to 50 .mu.m, more preferably from 1 to 10 .mu.m, and even more
preferably from 2 to 8 .mu.m.
The volume average particle diameter can be measured by laser type
particle diameter distribution measurement apparatus LA-920
(manufactured by Horiba Seisakusho), electrophoresis particle
diameter distribution measurement apparatus ELS-8000 (manufactured
by otsuka Denshi), or Multisizer III (manufactured by Coulter
Co.).
The resin (q) is contained in the resin particles (Q) of the
invention.
The resin (q) may be thermoplastic resin and thermosetting resin
and for example, vinyl resin, polyurethane resin, epoxy resin,
polyester, polyamide, polyimide, silicone type resin, phenol resin,
melamine resin, urea resin, aniline resin, ionomer resin,
polycarbonate resin, and mixtures of them may be used. From a
viewpoint that evenly fine and spherical resin fine particles can
be obtained easily, vinyl resin, polyurethane resin, epoxy resin,
polyester, and mixtures of them are preferable and vinyl resin,
epoxy resin, polyester, and mixtures of them are more
preferable.
Preferable resins for the resin (q), that is, vinyl resin,
polyurethane resin, epoxy resin, and polyester will be described
and with respect to other resins, they may be used similarly.
Practical examples of the resin (q) are those described below as
well as those described in International publication WO
03/106541.
The vinyl resin may include polymers obtained by homopolymerizing
or copolymerizing vinyl monomers. Conventionally known
polymerization catalysts may be used for the polymerization.
As vinyl monomers, the following compounds (1) to (10) can be
used.
(1) Vinyl Hydrocarbons:
(1-1) Aliphatic Vinyl Hydrocarbons: alkenes having 2 to 12 carbon
atoms (e.g., ethylene, propylene, butene, isobutylene, pentene,
heptene, diisobutylene, octene, dodecene, octadecene, and
.alpha.-olefins having 3 to 24 carbon atoms); and alkadienes having
4 to 12 carbon atoms (e.g., butadiene, isoprene, 1,4-pentadiene,
and 1,6-hexadiene).
(1-2) Alicyclic Vinyl Hydrocarbons: mono- or di-cycloalkenes having
6 to 15 carbon atoms (e.g., cyclohexene, vinylcyclohexene, and
ethylidenebicycloheptene); mono- or di-cycloalkadienes having 5 to
12 carbon atoms (e.g., (di)cyclopentadiene); terpenes (e.g.,
pinene, limonene, and indene); and the like.
(1-3) Aromatic Vinyl Hydrocarbons: styrene; hydrocarbyl(alkyl,
cycloalkyl, aralkyl, and/or alkenyl each having 1 to 24 carbon
atoms)-substituted styrene (e.g., .alpha.-methylstyrene,
vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, butylstyrene,
phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, and
divinylbenzene); vinylnaphthalene; and the like.
(2) Carboxyl Group-containing Vinyl Monomers and Salts thereof:
unsaturated monocarboxylic acids having 3 to 30 carbon atoms (e.g.,
(meth) acrylic acid, crotonic acid, isocrotonic acid and cinnamic
acid); unsaturated dicarboxylic acids having 3 to 30 carbon atoms
or anhydrides thereof (e.g., maleic acid (anhydride), fumaric acid,
itaconic acid, citraconic acid (anhydride), and mesaconic acid);
monoalkyl (having 1 to 24 carbon atoms) esters of unsaturated
dicarboxylic acids having 3 to 30 carbon atoms (e.g., monomethyl
ester of maleic acid, monooctadecyl ester of maleic acid, monoethyl
ester of fumaric acid, monobutyl ester of itaconic acid, glycol
monoether of itaconic acid); and the like.
Examples of salts of the carboxyl group-containing vinyl monomers
include alkali metal salts (e.g., sodium salts and potassium
salts), alkaline-earth metal salts (e.g., calcium salts and
magnesium salts), ammonium salts, amine salts, and quaternary
ammonium salts. The amine salts are not limited to any specific
ones as long as they are amine compounds, but primary amine salts
(e.g., ethylamine salts, butylamine salts, and octylamine salts),
secondary amine salts (e.g., diethylamine salts and dibutylamine
salts), and tertiary amine salts (e.g., triethylamine salts and
tributylamine salts) can be mentioned, for example. As the
quaternary ammonium salts, tetraethylammonium salts,
lauryltriethylammonium salts, and the like can be mentioned.
Specific examples of salts of the carboxyl group-containing vinyl
monomers include sodium acrylate, sodium methacrylate, monosodium
maleate, disodium maleate, potassium acrylate, potassium
methacrylate, monopotassium maleate, lithium acrylate, cesium
acrylate, ammonium acrylate, calcium acrylate, aluminum acrylate,
and the like.
(3) Sulfo Group-containing Vinyl Monomers and Salts thereof:
alkenesulfonic acids having 2 to 14 carbon atoms (e.g.,
vinylsulfonic acid, (meth)allylsulfonic acid, and
methylvinylsulfonic acid); styrenesulfonic acid and alkyl (having 2
to 24 carbon atoms) derivatives thereof (e.g.,
.alpha.-methylstyrenesulfonic acid);
sulfo(hydroxy)alkyl-(meth)acrylates having 5 to 18-carbon atoms
(e.g., sulfopropyl(meth)acrylate,
2-hydroxy-3-(meth)acryloxypropylsulfonic acid);
sulfo(hydroxy)alkyl(meth)acrylamides having 5 to 18 carbon atoms
(e.g., 2-(meth)acryloylamino-2,2-dimethylethanesulfonic acid,
2-(meth)acrylamide-2-methylpropanesulfonic acid); alkyl (having 3
to 18 carbon atoms) allylsulfosuccinic acids (e.g.,
propylallylsulfosuccinic acid, butylallylsulfosuccinic acid);
poly(n=2 to 30)oxyalkylene(oxyethylene, oxypropylene, oxybutylene:
homo, random, or block)mono(meth)acrylate sulfates (e.g., poly(n=5
to 15)oxyethylene monomethacrylate sulfate); polyoxyethylene
polycyclic phenyl ether sulfates (e.g., sulfates represented by the
general formula (1-1) or (1-2); sulfonic acids represented by the
general formula (1-3); salts thereof).
It is to be noted that counter ions mentioned with reference to
"(2) carboxyl group-containing vinyl monomers and salts thereof" or
the like are used for the salts.
##STR00001##
##STR00002##
##STR00003##
wherein R represents an alkyl group having 1 to 15 carbon atoms, AO
represents an oxyalkylene group having 2 to 4 carbon atoms, and
wherein when n is plural, oxyalkylene groups may be the same or
different, and when different, they may be random, block and/or
combination of random and block, Ar represents a benzen ring, n is
an integer of 1 to 50, and R' represents an alkyl group having 1 to
15 carbon atoms which may be substituted by a fluorine atom.
(4) Phosphono Group-containing Vinyl Monomers and Salts thereof:
(meth)acryloyloxyalkyl (having 1 to 24 carbon atoms) monophosphates
(e.g., 2-hydroxyethyl (meth)acryloyl phosphate and
phenyl-2-acryloyloxyethyl phosphate), and (meth)acryloyloxyalkyl
(having 1 to 24 carbon atoms)phosphonic acids (e.g.,
2-acryloyloxyethylphosphonic acid).
(5) Hydroxyl Group-containing Vinyl Monomers: hydroxystyrene,
N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate,
hydroxypropyl(meth)acrylate, polyethylene glycol
mono(meth)acrylate, (meth)allyl alcohol, crotyl alcohol, isocrotyl
alcohol, 1-butene-3-ol, propargyl alcohol, 2-hydroxyethyl propenyl
ether, and allyl ether of sucrose, and the like.
(6) Nitrogen-containing Vinyl Monomers:
(6-1) Amino Group-containing Vinyl Monomers: aminoethyl
(meth)acrylate, dimethylaminoethyl (meth)acrylate,
diethylaminoethyl (meth)acrylate, t-butylaminoethylmethacrylate,
N-aminoethyl (meth)acrylamide, (meth)allylamine, morpholinoethyl
(meth)acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine,
N,N-dimethylaminostyrene, methyl .alpha.-acetaminoacrylate,
vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone,
N-arylphenylenediamine, aminocarbazole, salts thereof, and the
like.
(6-2) Amide Group-containing Vinyl Monomers: (meth)acrylamide,
N-methyl(meth)acrylamide, N-butylacrylamide, diacetoneacrylamide,
N-methylol(meth)acrylamide, N,N'-methylene-bis(meth)acrylamide,
cinnamamide, N,N-dimethylacrylamide, and the like.
(6-3) Nitrile Group-containing Vinyl Monomers having 3 to 10 Carbon
Atoms: (meth)acrylonitrile, cyanostyrene, cyanoacrylate, and the
like.
(6-4) Quaternary Ammonium Cation Group-containing Vinyl Monomers:
quaternization products (obtained using a quaternizing agent such
as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl
carbonate or the like) of tertiary amine group-containing vinyl
monomers such as dimethylaminoethyl (meth)acrylate,
diethylaminoethyl (meth)acrylate, dimethylaminoethyl
(meth)acrylamide, diethylaminoethyl (meth)acrylamide, diallylamine,
and the like (e.g., dimethyldiallylammonium chloride and
trimethylallylammonium chloride).
(6-5) Nitro Group-containing Vinyl Monomers having 8 to 12 Carbon
Atoms: nitrostyrene and the like.
(7) Epoxy Group-containing Vinyl Monomers having 6 to 18 Carbon
Atoms: glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,
p-vinylphenyl oxide, and the like.
(8) Halogen-containing Vinyl Monomers having 2 to 16 Carbon Atoms:
vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride,
chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene,
tetrafluorostyrene, chloroprene, and the like.
(9) Vinyl Esters, Vinyl (Thio)Ethers, Vinyl Ketones, and Vinyl
Sulfones:
(9-1) Vinyl Esters having 4 to 16 Carbon Atoms: vinyl acetate,
vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl
phthalate, diallyl adipate, isopropenyl acetate, vinyl
methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl
(meth)acrylate, vinyl methoxyacetate, vinyl benzoate,
alkyl(meth)acrylates having an alkyl group containing 1 to 50
carbon atoms (e.g., methyl (meth)acrylate, ethyl (meth)acrylate,
butyl (meth)acrylate, dodecyl (meth)acrylate, heptadecyl
(meth)acrylate), dialkyl fumarates (whose two alkyl groups are
straight, branched or alicyclic groups having 2 to 8 carbon atoms),
dialkyl maleates (whose two alkyl groups are straight, branched or
alicyclic groups having 2 to 8 carbon atoms),
poly(meth)allyloxyalkanes (e.g., diallyloxyethane,
triallyloxyethane, tetraallyloxypropane), vinyl-based monomers
having a polyalkylene glycol chain [e.g., polyethylene glycol
(molecular weight: 300) mono(meth)acrylate, polypropylene glycol
(molecular weight: 500) monoacrylate, methyl alcohol-ethylene oxide
(10 mol) adduct (meth)acrylate, and lauryl alcohol-ethylene oxide
(30 mol) adduct (meth)acrylate], and poly(meth)acrylates (e.g.,
poly(meth)acrylates of polyhydric alcohols: ethylene glycol
di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene
glycol di(meth)acrylate), and the like.
(9-2) Vinyl (Thio)Ethers having 3 to 16 Carbon Atoms: vinyl methyl
ether, vinyl ethyl ether, vinyl butyl ether, vinyl 2-ethylhexyl
ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether,
methoxybutadiene, and phenoxystyrene, and the like.
(9-3) Vinyl Ketones having 4 to 12 Carbon Atoms (e.g., Vinyl Methyl
Ketone, Vinyl Ethyl Ketone, and Vinyl Phenyl Ketone): vinyl
sulfones having 2 to 16 carbon atoms (e.g., divinyl sulfide,
p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone,
divinyl sulfone, and divinyl sulfoxide), and the like.
(10) Other Vinyl Monomers: isocyanatoethyl (meth)acrylate,
m-isopropenyl-.alpha., .alpha.-dimethylbenzyl isocyanate, and the
like.
Among these vinyl monomers, vinyl hydrocarbons, carboxyl
group-containing vinyl monomers and salts thereof, sulfonic acid
group-containing vinyl monomers and salts thereof, hydroxyl
group-containing vinyl monomers, and nitrogen-containing vinyl
monomers are preferably used, more preferably, vinyl hydrocarbons,
carboxyl group-containing vinyl monomers and salts thereof, and
sulfonic acid group-containing vinyl monomers and salts thereof,
even more preferably aromatic vinyl-based hydrocarbons, carboxyl
group-containing vinyl monomers and salts thereof, and sulfonic
acid group-containing vinyl monomers and salts thereof.
Among vinyl resins, as polymers obtained by copolymerizing vinyl
monomers (copolymers of vinyl monomers), polymers obtained by
copolymerizing two or more of the monomers mentioned in (1) to (10)
in any ratio are used. Examples of such copolymers include
styrene-(meth)acrylate copolymer, styrene-butadiene copolymer,
(meth)acrylic acid-(meth)acrylate copolymer, styrene-acrylonitrile
copolymer, styrene-maleic acid (anhydride) copolymer,
styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic
acid-divinylbenzene copolymer, and styrene-styrenesulfonic
acid-(meth)acrylate copolymer, and the like.
Since the composite resin particles are preferable to be produced
by a production method described below, that is a production method
involving a step of dispersing the resin (p), a precursor (p0) of
the resin (p), or a their solution in a water-based dispersion
containing the resin fine particles (Q), the resin fine particles
(Q) are preferable to be dispersed in a water-based dispersion.
Accordingly, the resin (Q) is preferable not to be dissolved
completely in water at least under the condition for forming the
water-based dispersion. Therefore, in the case the vinyl resin is a
copolymer, although it depends on the types of monomers to be
selected, the ratio of a hydrophobic monomer and a hydrophilic
monomer composing the vinyl resin is preferably 10% or higher of
the hydrophobic monomer in the total weight of the monomers and
more preferably 30% or higher. If the ratio of the hydrophobic
monomer is 10% or lower, the vinyl resin tends to be water-soluble
and the particle diameter evenness of the composite resin particles
tends to be lowered.
Herein, the hydrophilic monomer means a monomer soluble in water at
an optional ratio and the hydrophobic monomer means a monomer other
than the former (a monomer which may be dissolved in an amount of
less than 100 g in 100 g of water at 25.degree. C.) (hereinafter,
it may be same for resins below).
As the polyester are usable polycondensation products of polyols
with polycarboxylic acids, their anhydrides or esters of lower
alkyl (alkyl having 1 to 4 carbon atoms).
A conventionally known polycondensation catalyst may be used for
the polycondensation reaction.
Examples usable as the polyols are diols (11) and tri- to octa- or
higher hydric polyols (12).
Examples usable as polycarboxylic acids, their anhydrides and
esters of lower alkyl are dicarboxylic acids (13), tri- to hexa- or
higher valent polycarboxylic acids (14), their anhydrides and lower
alkyl esters.
Examples of the diols (11) and tri- to octa- or higher hydric
polyols (12) are those exemplified for the polyhydric alcohols
composing the above-mentioned polyol component.
Among them are aliphatic polyhydric alcohols and AO adducts of
novolak resins preferable and AO adducts of novolak resins more
preferable.
Examples usable as the dicarboxylic acids (13) are the
above-mentioned aliphatic (including alicyclic) dicarboxylic acids
and aromatic dicarboxylic acids.
Among them are alkenedicarboxylic acids and aromatic dicarboxylic
acids preferable and aromatic dicarboxylic acids more
preferable.
Examples usable as the tri- to hexa- or higher valent
polycarboxylic acids (14) are the above-mentioned aliphatic
(including alicyclic) polycarboxylic acids and aromatic
polycarboxylic acids.
Examples usable as the acid anhydrides of the dicarboxylic acids
(13) and the tri- to hexa- or higher valent polycarboxylic acids
(14) are trimellitic anhydride and pyromellitic anhydride. Examples
of their lower alkyl esters are methyl ester, ethyl ester, and
isopropyl ester.
For the polyester, diols, tri- to octa- or higher hydric polyols,
dicarboxylic acids, tri- to hexa- or higher valent polycarboxylic
acids, and their mixtures may be used in form of a mixture at any
optional ratio. The equivalent ratio [OH]/[COOH] of the hydroxyl
group [OH] and carboxyl group [COOH] is preferably (2/1) to (1/2),
more preferably (1.5/1) to (1/1), and even more preferably (1.3/1)
to (1.02/1).
Also, the ester group equivalent in the polyester (the molecular
weight per an equivalent of ester group) is preferably in a range
from 50 to 2,000, more preferably from 60 to 1,000, and even more
preferably from 70 to 500.
As the polyurethane are polyaddition products of polyisocyanates
(15) and active hydrogen-containing compound (.beta.1) [e.g. water,
diols (11), tri- to octa- or higher hydric polyols (12),
dicarboxylic acids (13), tri- to hexa- or higher valent
polycarboxylic acids (14), polyamines (16), and polythiols (17)]
usable.
Conventionally known polyaddition catalysts may be used for the
polyaddition reaction.
Examples of the polyisocyanates (15) include aromatic
polyisocyanates having 6 to 20 carbon atoms (exclusive of the
carbon in an NCO group; the same applies to the following
description), aliphatic polyisocyanates having 2 to 18 carbon
atoms, alicyclic polyisocyanates having 4 to 15 carbon atoms,
araliphatic polyisocynates having 8 to 15 carbon atoms, and
modification products of these polyisocyanates (e.g., modified
polyisocyanates having urethane, carbodiimide, allophanate, urea,
biuret, urethodione, urethoimine, isocyanurate, or oxazolidone
groups), mixtures of two or more of them, and the like.
Examples of the aromatic polyisocyanates include 1,3-or
1,4-phenylene diisocyanate, 2,4-or 2,6-tolylene diisocyanate (TDI),
crude TDI, 2,4'-or 4,4'-diphenylmethane diisocyanate (MDI), crude
MDI [phosgenide of crude diaminophenylmethane [a condensation
product of formaldehyde with aromatic amine (aniline) or a mixture
containing such aromatic amine; a mixture of diaminodiphenylmethane
and a small amount (e.g., 5 to 20%) of polyamine having 3 or more
amino groups]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene
diisocyante, 4,4',4''-triphenylmethane triisocyanate, m-or
p-isocyanatophenylsulfonyl isocyanate, mixtures of two or more of
them, and the like.
Examples of the aliphatic polyisocyanates include ethylene
diisocyanate, tetramethylene diisocyanate,
hexamethylenediisocyanate (HDI), dodecamethylenediisocyanate,
1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene
diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate,
bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate,
2-isocyanatoethyl-2,6-diisocyanatohexanoate, mixtures of two or
more of them, and the like.
Examples of the alicyclic polyisocyanates include isophorone
diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate
(hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene
diisocyanate (hydrogenated TDI),
bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-or
2,6-norbornane diisocyanate, mixtures of two or more of them, and
the like.
Examples of the araliphatic polyisocyanates include m-or p-xylylene
diisocyanate (XDI), .alpha., .alpha., .alpha.',
.alpha.'-tetramethylxylylene diisocyanate (TMXDI), mixtures of two
or more of them, and the like.
Examples of the modification products of polyisocyanates include
modified polyisocyanates having urethane, carbodiimide,
allophanate, urea, biuret, urethodione, urethoimine, isocyanurate
and/or oxazolidone groups, such as modified MDI (e.g.,
urethane-modified MDI, carbodiimide-modified MDI, and
trihydrocarbylphosphate-modified MDI), urethane-modified TDI,
mixtures of two or more of them [e.g., a mixture of the modified
MDI and the urethane-modified TDI (isocyanate-containing
prepolymer)], and the like.
Among these polyisocyanates, aromatic polyisocyanates, aliphatic
polyisocyanates, and alicyclic polyisocyanates are preferably used,
more preferably TDI, MDI, HDI, hydrogenated MDI, and IPDI.
As polyamines (16), aliphatic polyamines having 2 to 18 carbon
atoms, aromatic polyamines having 6 to 20 carbon atoms, and the
like can be used.
As aliphatic polyamines having 2 to 18 carbon atoms, (1) aliphatic
polyamines, (2) alkyl (having 1 to 4 carbon atoms)-or hydroxyalkyl
(having 2 to 4 carbon atoms)-substituted aliphatic polyamines
mentioned above, (3) alicyclic or heterocycle-containing aliphatic
polyamines, (4) aromatic ring-containing aliphatic amines having 8
to 15 carbon atoms, and the like can be used.
(1) Examples of the aliphatic polyamines include alkylenediamines
having 2 to 12 carbon atoms (e.g., ethylenediamine,
propylenediamine, trimethylenediamine, tetramethylenediamine, and
hexamethylenediamine), polyalkylene (having 2 to 6 carbon atoms)
polyamines [e.g., diethylenetriamine, iminobispropylamine,
bis(hexamethylene)triamine, triethylenetetramine, and
pentaethylenehexamine], and the like.
(2) Examples of the alkyl (having 1 to 4 carbon atoms)-or
hydroxyalkyl (having 2 to 4 carbon atoms)-substituted aliphatic
polyamines mentioned above include dialkyl (having 1 to 3 carbon
atoms) aminopropylamine, trimethylhexamethylenediamine,
aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, and
methyliminobispropylamine, and the like.
(3) Examples of the alicyclic or heterocycle-containing aliphatic
polyamines include alicyclic polyamines having 4 to 15 carbon atoms
{e.g., 1,3-diaminocyclohexane, isophoronediamine, menthenediamine,
4,4'-methylenedicyclohexanediamine (hydrogenated
methylenedianiline), and
3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane}, and
heterocyclic polyamines having 4 to 15 carbon atoms [e.g.,
piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, and
1,4-bis(2-amino-2-methylpropyl)piperazine], and the like.
(4) Examples of the aromatic ring-containing aliphatic amines
(having 8 to 15 carbon atoms) include xylylenediamine,
tetrachloro-p-xylylenediamine, and the like.
As the above-mentioned aromatic polyamines having 6 to 20 carbon
atoms, (1) unsubstituted aromatic polyamines, (2) aromatic
polyamines nuclearly substituted by one or more alkyl groups
(having 1 to 4 carbon atoms, such as methyl, ethyl, n-or i-propyl
and butyl), (3) aromatic polyamines having one or more
electron-attracting groups such as halogen (e.g., Cl, Br, I, and
F), alkoxy groups (e.g., methoxy and ethoxy), and a nitro group,
and (4) secondary amino group-containing aromatic polyamines, and
the like can be used.
(1) Examples of the unsubstituted aromatic polyamines include 1,2-,
1,3-or 1,4-phenylenediamine, 2,4'-or 4,4'-diphenylmethanediamine,
crude diphenylmethanediamine (polyphenylpolymethylenepolyamine),
diaminodiphenyl sulfone, benzidine, thiodianiline,
bis(3,4-diaminophenyl) sulfone, 2,6-diaminopyridine,
m-aminobenzylamine, triphenylmethane-4,4',4''-triamine,
naphthylenediamine, mixtures of two or more of them, and the
like.
[2] Examples of aromatic polyamines having a nuclear-substituting
alkyl group (e.g. alkylhavingl to 4 carbon atoms such as methyl,
ethyl, n-or iso-propyl and butyl) are 2,4-or 2,6-tolyelendiamine,
crude tolylenediamine, diethyltolylenediamine,
4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis(o-toluidine),
dianisidine, 1,3-dimethyl-2,4-diaminobenzene, and their
mixtures.
(3)Examples of aromatic polyamines having a nuclear-substituting
electron attractive group (e.g. halogen such as Cl, Br, I, and F;
alkoxy group such as methoxy and ethoxy; and nitro group) are
methylene bis(o-chloroaniline), 4-chloro-o-phenylenediamine,
2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, and
4-bromo-1,3-phenylenediamine,
(4) Examples of the secondary amino group-containing aromatic
polyamines include aromatic polyamines obtained by replacing some
or all of --NH.sub.2 groups in the aromatic polyamines (1) to (3)
with --NH--R' groups (wherein R' represents an alkyl group such as
a lower alkyl group having 1 to 4 carbon atoms e.g., methyl, ethyl,
or the like), such as 4,4'-di(methylamino)diphenylmethane, and
1-methyl-2-methylamino-4-aminobenzene, and the like; polyamide
polyamines such as low molecular-weight polyamide polyamines
obtained by condensation of dicarboxylic acids (e.g., dimer acid)
with excess (that is, 2 or more mols per mol of the acid)
polyamines (e.g., the alkylenediamines and the
polyalkylenepolyamines mentioned above); polyether polyamines such
as hydrides of cyanoethylation products of polyether polyols (e.g.,
polyalkylene glycol); and the like.
As polythiols (17), dithiols having 2 to 24 carbon atoms, tri-to
hexa-or higher valent polythiols having 5 to 30 carbon atoms, and
the like can be used.
Examples of dithiols include ethylenedithiol, 1,4-butanedithiol,
1,6-hexanedithiol, and the like.
Examples of polythiols include Capcure-3800 (manufactured by Japan
Epoxy Resins Co., Ltd.), polyvinylthiol, and the like.
Among these active hydrogen-containing compounds (.beta.1), water,
the diols (11), the polyols (12), the dicarboxylic acids (13), and
the polyamines (16) are preferably used, more preferably water, the
diols (11), the polyols (12), and the polyamines (16), even more
preferably the diols (11), the polyols (12), and the polyamines
(16).
As epoxy resins, ring-opening polymerization products of
polyepoxides (18), polyaddition products of the polyepoxides (18)
and the active hydrogen-containing compounds (.beta.1), and curing
reaction products of the polyepoxides (18) and acid anhydrides of
the dicarboxylic acids (13) or the polycarboxylic acids (14) having
3 to 4 or more carboxyl groups, and the like can be used.
In ring-opening polymerization reaction, polyaddition reaction, and
curing reaction, a well-known catalyst or the like can be used.
The polyepoxides (18) are not particularly limited if they have two
or more epoxy groups in a molecule and in terms of mechanical
properties of cured products, those having 2 to 6 epoxy groups in a
molecule are preferable.
The epoxy equivalent (molecular weight per one epoxy group) of the
polyepoxides (18) is preferably in a range from 65 to 1000, more
preferably from 70 to 500, and even more preferably from 90 to 300.
That is, the upper limit of the epoxy equivalent is preferably
1000, more preferably 500, and even more preferably 300, and
similarly the lower limit is preferably 65, more preferably 70, and
even more preferably 90. If the epoxy equivalent exceeds 1000, the
crosslinking structure tends to be loosened and thus the physical
properties such as water-proofness, chemical resistance, and
mechanical strength of the cured products tend to be deteriorated
and on the other hand, those having an epoxy equivalent lower than
65 are difficult to be made available (difficult to be
synthesized).
As polyepoxides (18), aromatic polyepoxides, heterocycle-containing
polyepoxides, alicyclic polyepoxides, aliphatic polyepoxides, and
the like can be used.
As aromatic polyepoxides, glycidyl ethers of polyhydric phenols,
glycidyl esters of polyhydric phenols, glycidyl aromatic
polyamines, and glycidylation products of aminophenols, and the
like can be used.
Examples of polyhydric phenol glycidyl ethers are bisphenol F
diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B
diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S
diglycidyl ether, and glycidyl ethers of phenol or cresol-novolak
resin.
Examples of the glycidyl esters of polyhydric phenols include
diglycidyl phthalate, diglycidyl isophthalate, diglycidyl
terephthalate, and the like.
Examples of the glycidyl aromatic polyamines include
N,N-diglycidylaniline, N,N,N',N'-tetraglycidylxylylenediamine, and
N,N,N',N'-tetraglycidyldiphenylmethanediamine, and the like.
Further, the epoxides include triglycidyl ether of p-aminophenol,
diglycidyl urethane compounds obtained by the addition reaction of
tolylene diisocyanate or diphenylmethane diisocyanate and glycidol,
and diglycidyl ethers of alkylene oxide (ethylene oxide or
propylene oxide) (2 to 20 mol) adducts of bisphenol A (e.g.,
diglycidyl ether of EO (4 mol) adduct of bisphenol A).
As heterocyclic polyepoxides, trisglycidylmelamine can be used.
As alicyclic polyepoxides, vinylcyclohexene dioxide, limonene
dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether,
ethylene glycol bisepoxydicyclopentyl ether, dimer acid diglycidyl
ester, and nuclear hydrogenation products of aromatic polyepoxides
(e.g., hydrogenated bisphenol F diglycidyl ether and hydrogenated
bisphenol A diglycidyl ether) can be used, for example.
As aliphatic polyepoxides, polyglycidyl ethers of polyhydric
aliphatic alcohols, polyglycidyl esters of polyvalent fatty acids,
glycidyl aliphatic amines, and the like can be used.
Examples of the polyglycidyl ethers of polyhydric aliphatic
alcohols include ethylene glycol diglycidyl ether, propylene glycol
diglycidyl ether, tetramethylene glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl
ether, polypropylene glycol diglycidyl ether, polytetramethylene
glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether,
pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether,
polyglycerol polyglycidyl ether, and the like.
Examples of the polyglycidyl esters of polyvalent fatty acids
include diglycidyl oxalate, diglycidyl maleate, diglycidyl
succinate, diglycidyl adipate, and the like.
Examples of the glycidyl aliphatic amines include
N,N,N',N'-tetraglycidyl hexamethylenediamine, and
N,N,N',N'-tetraglycidyl ethylenediamine, and the like.
The aliphatic polyepoxides include (co)polymers of diglycidyl
ethers and glycidyl(meth)acrylates.
Among these polyepoxides, aliphatic polyepoxy compounds and
aromatic polyepoxy compounds are preferably used. In the present
invention, the polyepoxides may be used in combination of two or
more of them.
Mn of the resin (q) is preferably in a range from 200 to 5,000,000,
more preferably from 2,000 to 1,000,000, and even more preferably
from 3,000 to 500,000.
Mn and the weight average molecular weight in the eighth invention
can be measured by gel permeation chromatography (GPC) (THF
solution, standardized substance: polystyrenes). Hereinafter,
weight average molecular weight is abbreviated as Mw.
The SP value of the resin (q) is preferably in a range from 7 to
18, more preferably from 8 to 16, and even more preferably from 8.5
to 14.
The SP value is calculated by the method described in Polymer
Engineering and Science, February, 1974, Vol. 14, No. 2, p.
147-154.
In the case the resin (q) is a crystalline polymer, the melting
point of the resin (q) is preferably 35.degree. C. or higher, more
preferably from 40 to 250.degree. C., and even more preferably from
50 to 200.degree. C.
The melting point is measured by DSC (heating speed: 20.degree.
C./min.).
Further, to improve the heat resistance, water-proofness, chemical
resistance, and evenness of particle diameter of the composite
resin particles, crosslinking structure may be introduced into the
resin (q). The crosslinking structure may be any crosslinking state
such as covalent bonding, coordination bonding, ion bonding,
hydrogen bonding and the like.
A common method may be employed for the method for introducing the
crosslinking structure.
The acid value of the resin (q) is preferably 0 to 400, more
preferably from 1 to 300, furthermore preferably 1 to 200, and even
more preferably from 5 to 50.
In the case the composite resin particles are used for a coating
material, an additive for a coating, a powder coating, a resin for
slush molding, or a hot-melt adhesive, in terms of the adhesion to
a substrate and leveling property, the acid value of the resin (q)
is preferably from 0 to 400, more preferably from 1 to 300, further
more preferably from 1 to 200, and even more preferably from 1 to
100.
In the case of using them for a toner to be used for
electrophotography, electrostatic recording, and electrostatic
printing, in terms of the electrostatic property and fixing
property on paper, the acid value of the resin (q) is preferably
from 0 to 400, more preferably from 1 to 300, and even more
preferably from 1 to 200.
The resin fine particles (Q) are required to have strength
sufficient not to be broken by shearing at the time of dispersing
the resin (p), the precursor (p0) of the resin (p), and/or their
solutions; to be hardly dissolved or swollen in water; and also to
be hardly dissolved or swollen in the resin (p), the precursor (p0)
of the resin (p), and/or their solutions.
From a viewpoint of prevention of the resin fine particles (Q) from
dissolving or swelling in water or a solvent to be used at the time
of dispersion, the molecular weight (Mn, Mw), SP value,
crystallinity, and crosslinking structure of the resin (p) are
preferable to be adjusted properly.
Tg of the resin (Q) is preferably in a range from 0 to 300.degree.
C., more preferably from 20 to 250.degree. C., furthermore
preferably from 45 to 200.degree. C., and even more preferably from
50 to 200.degree. C. in terms of the shape, particle size evenness,
powder fluidity, heat resistance (at the time of storage) and
stress resistance of the composite resin particles.
Tg in the eighth invention is calculated by DSC (differential
scanning calorimetry, heating speed 20.degree. C./min.)
The resin fine particles (Q) may contain the above-mentioned
additive (T) (e.g. various kinds of additives such as a filler, a
colorant, a plasticizer, a release agent, a charge control agent,
an ultraviolet absorbent, an antioxidant, an antistatic agent, a
flame retardant, an antibacterial agent, and a preserver) other
than the resin (q).
The content of the additive (T) may be adjusted properly depending
on the various uses and on the basis of the weight of the resin
fine particles (Q), it is preferably in a range from 0.01 to 150%,
more preferably from 0.2 to 100%, and even more preferably from 0.5
to 80%.
The production method of the resin fine particles (Q) is not
particularly limited and for example, the following methods [1] to
[8] can be exemplified. The methods [1] to [8] are methods of
obtaining a water-based dispersion of the resin fine particles (Q)
and the water-based dispersion of the resin fine particles (Q) may
be used as it is for producing composite resin particles of the
invention or the resin fine particles (Q) alone may be separated
from the water-based dispersion or the resin fine particles (Q) may
be separated during the production of the water-based dispersion. A
filtration method, a decantation method, and a centrifugal
separation method may be used as the separation method. [1] in the
case of a vinyl resin: a method of directly producing a water-based
dispersion of the resin fine particles (Q) by polymerizing monomers
as starting materials in the presence of a polymerization catalyst
using such method as a suspension polymerization method, an
emulsion polymerization method, a seed polymerization method, or a
dispersion polymerization method; [2] in the case of a poly
addition resin or poly condensation resin such as polyester,
polyurethane, and epoxy resin; a method of producing a water-based
dispersion of the resin fine particles (Q) by dispersing a
precursor (p0) of the resin (p) [e.g. a monomer of the
above-mentioned diol (11), polyol (13), dicarboxylic acid (14),
polyisocyanate (15), polyamine (16), polythiol (17), or polyepoxide
(18), or oligomer having Mn of 1000 or lower which is dimer or
higher reaction products of the monomer (including reaction
products of the same kind monomer or of two or more kinds of
monomers)] or a solution of the precursor (p0) in a water-based
medium in the presence of a dispersant and successively heating the
obtained mixture or adding a curing agent (e.g. a compound having
at least two functional groups reactive on the precursor in one
molecule) to the obtained mixture for curing; [3] in the case of a
polyaddition resin or polycondensation resin such as polyester,
polyurethane, and epoxy resin; a method involving phase inversion
emulsification by dissolving a proper emulsifier in a precursor
(p0) (e.g. a monomer or an oligomer) or a solution of the precursor
(p0) (a liquid is preferable, or liquefied by heating) and further
adding water; [4] a method involving previously producing a resin
(q) by polymerization reaction (e.g. any polymerization reaction
manners such as addition polymerization, ring opening
polymerization, polyaddition, addition condensation, and
polycondensation), grinding the previously produced resin (q) by a
mechanically rotating or jetting type finely grinding pulverizer,
successively carrying out classification for obtaining the resin
fine particles (Q), and then dissolving the particles in water in
the presence of a proper dispersant; [5] a method involving
previously producing a solution of a resin (q) by polymerization
reaction (e.g. any polymerization reaction manners such as addition
polymerization, ring opening polymerization, polyaddition, addition
condensation, and polycondensation), spraying the solution of the
resin (q) for removing the solvent from the solution of the resin
(q) and obtaining the resin fine particles (Q), and then dissolving
the particles in water in the presence of a proper dispersant; [6]
a method involving previously producing a solution of a resin (q)
by polymerization reaction (e.g. any polymerization reaction
manners such as addition polymerization, ring opening
polymerization, polyaddition, addition condensation, and
polycondensation), precipitating resin fine particles either by
adding a poor solvent [a solvent in which not more than 1% of the
resin (q) is dissolved at 25.degree. C.] to the previously produced
solution of the resin (q) or by cooling the solution of the resin
(q) which is previously dissolved and heated in a solvent,
successively removing the solvent for obtaining the resin fine
particles (Q), and then dissolving the obtained resin fine
particles (Q) in water in the presence of a proper dispersant; [7]
a method involving previously producing a solution of a resin (q)
by polymerization reaction (e.g. any polymerization reaction
manners such as addition polymerization, ring opening
polymerization, polyaddition, addition condensation, and
polycondensation), dispersing the solution of the resin (q) in a
water-based medium in the presence of a proper dispersant, and
removing the solvent by heating or reducing the pressure; and [8] a
method involving previously producing a solution of a resin (q) by
polymerization reaction (e.g. any polymerization reaction manners
such as addition polymerization, ring opening polymerization,
polyaddition, addition condensation, and polycondensation), adding
a proper emulsifier to the solution of the resin (q), carrying out
phase inversion emulsification by adding water, and removing the
solvent by heating or reducing the pressure.
Methods [1] to [3], [7], and [8] are preferable, methods [1] to [3]
and [7] are more preferable, and methods [2], [3], and [7] are even
more preferable among the above-mentioned methods [1] to [8].
In the above-mentioned methods [1] to [8], a conventionally known
surfactant (S) and water-soluble polymer (T) may be used as the
emulsifier and dispersant.
In the case the surfactant (S) is used, the use amount is
preferably in a range from 0.1 to 20%, more preferably from 1 to
15%, and even more preferably from 2 to 10% on the basis of the
weight of the resin (p) and precursor (p0).
In the case the water-soluble polymer (T) is used, the use amount
is preferably in a range from 0.01 to 20%, more preferably from 0.1
to 15%, and even more preferably from 0.2 to 10% on the basis of
the weight of the resin (p) and precursor (p0).
Further, a solvent (U) and/or a plasticizer (V) may be used in
combination as assisting agents for emulsification or
dispersion.
In the case the solvent (U) is used, the use amount is preferably
in a range from 0.1 to 20%, more preferably from 0.5 to 15%, and
even more preferably from 1 to 10% on the basis of the weight of
the resin (p) and precursor (p0).
In the case the plasticizer (V) is used, the use amount is
preferably in a range from 0.01 to 10%, more preferably from 0.1 to
8%, and even more preferably from 1.0 to 5% on the basis of the
weight of the resin (p) and precursor (p0).
The solvent (U) and/or plasticizer (V) may be added to water or to
the resin (p) during emulsification and dispersion based on the
necessity.
Examples of the surfactant (S), water-soluble polymer (T), solvent
(U) and plasticizer (V) are those described above.
Preferable examples of the water-soluble polymer (T) are cellulose,
starch, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene
glycol, and polymer containing acrylic acid (salts).
In terms of the easiness for removing the solvent, preferable
examples of the solvent (U) are aromatic hydrocarbon solvents,
halogen solvents, ester or ester ether solvents, ketone solvents,
and alcohol solvents, and more preferable examples are ester or
ester ether solvents, ketone solvents, and alcohol solvents.
The particle diameter of the resin fine particles (Q) is generally
smaller than that of resin particles (P) and in terms of the
particle size evenness, the particle diameter ratio [(volume
average particle diameter of (Q))/(volume average particle diameter
of (P))] is preferably in a range from 0.001 to 0.3. The lower
limit of the particle diameter ratio is more preferably 0.003 and
the upper limit is more preferably 0.25. If the particle diameter
ratio is larger than 0.3, since the resin particles (Q) are not
efficiently adsorbed on the resin particles (P), the particle
diameter distribution of the obtained composite resin particles
tends to be wide.
The volume average particle diameter of the resin fine particles
(Q) may properly be adjusted within the above-mentioned particle
diameter ratio so as to obtain a desired particle diameter of the
composite resin particles.
The volume average particle diameter of the resin fine particles
(Q) is, in general, preferably in a range from 0.0005 to 30 .mu.m.
The upper limit is more preferably 20 .mu.m and even more
preferably 10 .mu.m and the lower limit is more preferably 0.01
.mu.m, furthermore preferably 0.02 .mu.m, and even more preferably
0.04 .mu.m. However, in the case of obtaining composite resin
particles with a volume average particle diameter of 1 .mu.m, it is
preferably in a range from 0.0005 to 0.3 .mu.m and more preferably
from 0.001 to 0.2 .mu.m: in the case of obtaining 10 .mu.m of (C),
it is preferably in a range from 0.005 to 3 .mu.m and more
preferably from 0.05 to 2 .mu.m: and in the case of obtaining 100
.mu.m of composite resin particles, it is preferably in a range
from 0.05 to 30 .mu.m and more preferably from 0.1 to 20 .mu.m. The
volume average particle diameter can be measured by laser type
particle diameter distribution measurement apparatus LA-920
(manufactured by Horiba Seisakusho), electrophoresis particle
diameter distribution measurement apparatus ELS-8000 (manufactured
by Otsuka Denshi), or Coulter counter [e.g. trade name: Multisizer
III (manufactured by Coulter Co.)].
A production method of the composite resin particles of the
invention is not particularly limited, however the method may be
carried out by dispersing an additive, if necessary, and the resin
(p) or its organic solvent solution in a water-based dispersion (W)
of the resin fine particles (Q) containing an additive, if
necessary, and the resin (q) for forming the resin particles (P) of
the resin (p) in the water-based dispersion of the resin fine
particles (Q) and thus obtaining a water-based resin dispersion of
the composite resin particles comprising the resin particles (P)
and the resin fine particles (Q) adhering to the surface of the
particles (P).
Or, the method may be carried out by dispersing a precursor (p0) of
the resin (p) or its organic solvent solution in the water-based
dispersion of the resin fine particles (Q) of the resin (q),
causing reaction of the precursor (p0), and thereby forming the
resin particles (P) of the resin (p) and obtaining a water-based
resin dispersion containing resin particles comprising the resin
particles (P) and the resin fine particles (Q) adhering to the
surface of the particles (P).
The water-based dispersion of the composite resin particles
obtained by the above-mentioned methods is subjected to
solid-liquid separation (if necessary, solid-liquid separation is
repeated by adding water or the like) and the separated solid is
dried for removing the water-based medium to obtain the composite
resin particles of the invention.
A dispersing apparatus and/or an apparatus for applying shearing
force to be used in the above-mentioned production methods is not
particularly limited and commonly commercialized emulsifying
apparatuses and/or dispersing apparatuses may be used and examples
of commercialized apparatuses are as exemplified above.
Among the exemplified ones, in terms of the evenness of the
particle diameter, APV Gaulin, homogenizer, TK Auto-homomixer,
Ebara Milder, TK Filmix, and TK Pipeline Homomixer are preferable
and TK Auto-homomixer, Ebara Milder, TK Filmix, and TK Pipeline
Homomixer are more preferable, and TK Auto-homomixer, TK Filmix,
and TK Pipeline Homomixer are even more preferable.
In the above-mentioned production methods, in terms of the high
evenness of the particle diameter and storage stability of the
composite resin particles, the weight ratio (Q/P) of the resin fine
particles (Q) and resin particles (P) is preferably (0.01 to
60)/(40 to 99.99), more preferably (0.05 to 55)/(45 to 99.95), and
even more preferably (0.1 to 50)/(50 to 99.9). That is, the upper
limit of the weight ratio (P/B) is preferably 60/40, more
preferably 55/45, and even more preferably 50/50 and similarly the
lower limit of the weight ratio (P/B) is preferably 0.01/99.99,
more preferably 0.05/99.95, and even more preferably 0.1/99.9.
Accordingly, the resin (q), resin (p), and precursor (p0) are
preferable to be used so as to adjust the weight ratio within the
above-mentioned range.
The use amount of the water-based medium to 100 part of the resin
(p) and/or precursor (p0) is preferably in a range from 50 to 2,000
part, more preferably from 100 to 1,000 part, and even more
preferably from 100 to 500 part. That is, the upper limit of the
use amount of the water-based medium is preferably 2,000 part, more
preferably 1,000 part, and even more preferably 500 part and
similarly, the lower limit is preferably 50 part and more
preferably 100 part. If it is less than 50 part, the dispersion
state of the resin (q) tends to be worsened and if it exceeds 2,000
part, it is not preferable in terms of the economy.
The use amount of the water-based medium to 100 part of the resin
(p) is preferably in a range from 50 to 2,000 part, more preferably
from 100 to 1,000 part, and even more preferably from 100 to 500
part. If it is less than 50 part, the dispersion state of the resin
(q) tends to be worsened and if it exceeds 2,000 part, it is not
preferable in terms of the economy.
The water-based medium may be used without any limit if it is a
liquid containing water as an indispensable component and water, an
aqueous solution of a solvent, an aqueous solution of the
surfactant (S), an aqueous solution of the water-soluble polymer
(T), and a mixture of them may be used.
Examples of the solvent to be used may be ester or ester ether
solvents, ether solvents, ketone solvents, alcohol solvents, amide
solvents, sulfoxide solvents, heterocyclic compound solvents, and
mixed solvents of two or more kinds of them among the
above-mentioned solvents (U).
In the case a solvent is contained, the content of the solvent is
preferably from 1 to 80%, more preferably from 2 to 70%, and even
more preferably 5 to 30% on the basis of the weight of the
water-based medium.
In the case the surfactant (S) is used, the content of the
surfactant is preferably from 0.1 to 20%, more preferably from 0.5
to 10%, and even more preferably 1.0 to 8% on the basis of the
weight of the water-based medium.
In the case the water-soluble polymer (T) is used, the content of
the water-soluble polymer is preferably from 0.01 to 10%, more
preferably from 0.05 to 7%, and even more preferably 0.1 to 5% on
the basis of the weight of the water-based medium.
The volume average particle diameter (DV) of the composite resin
particles can be adjusted by properly adjusting the volume average
particle diameter (DVQ) of the resin fine particles (Q). For
example, in the case of obtaining composite resin particles with 1
.mu.m (DV), (DVQ) is preferably from 0.0005 to 0.4 .mu.m and more
preferably from 0.001 to 0.3 .mu.m, and in the case of obtaining
composite resin particles with 10 .mu.m (DV) or larger, (DVQ) is
preferably from 0.005 to 4 .mu.m and more preferably from 0.05 to
0.3 .mu.m.
At the time of dispersing the resin (q) and/or the precursor (p0)
in the water-based medium of the resin fine particles (Q), the
resin (q) and the precursor (p0) are preferably liquids. In the
case the resin (q) and the precursor (p0) are solid in a normal
temperature, they may be dispersed in a liquid state at a high
temperature equal to or higher than the melting point or solutions
of the resin (q) and the precursor (p0) may be used.
In terms of the evenness of the particle diameter, the viscosity of
the resins (p), (q) and the precursor (p0) and their solutions is
preferably from 10 to 50,000 mPaS, more preferably from 100 to
30,000 mPaS, and even preferably from 200 to 20,000 mPaS. That is,
the upper limit of the viscosity is preferably 50,000 mPaS, more
preferably 30,000 mPaS, and even preferably 20,000 mPaS, and
similarly the lower limit is preferably 10 mPaS, more preferably
100 mPaS, and even preferably from 200 mPaS.
The viscosity is measured by a rotor type viscometer (e.g. BL type
viscometer, BM type viscometer, BH type viscometer, manufactured by
Tokyo Keiki Co.) at 25.degree. C. and 30 rpm.
The temperature at the time of dispersion is preferably in a range
from 0 to 150.degree. C., more preferably from 5 to 98.degree. C.,
and even preferably from 10 to 60.degree. C. In the case it exceeds
100.degree. C., the temperature shows under pressurized condition.
In the case the viscosity of the dispersion is high, it is
preferable that the temperature is increased to lower the viscosity
in a preferably range and then the emulsification and dispersion
are carried out.
The solvent to be used for the solution of the resin (p) and the
solution of the precursor (p0) is not particularly limited if it
can dissolve the resin and precursor at a normal temperature or
under heating temperature and for example, those same as
exemplified for the solvent (U) may be used. Among them, although
depending on the types of the resin (p) and the precursor (p0),
those having difference of SP value from that of the resin (p) and
the precursor (p0) within 3 or less are preferable and more
preferably solvents which can dissolve the resin (p) but hardly
dissolve or swell the resin particles (Q) of the resin (Q) in terms
of the evenness of the particle diameter of the composite resin
particles.
In the above-mentioned method, an emulsifier and a dispersant can
be used and the above-mentioned surfactant (S) and water-soluble
polymer (T) may be used as the emulsifier and dispersant. Further,
the above-mentioned solvent (U) and plasticizer (V) are also usable
in combination as assisting agents for the emulsifier and
dispersant.
In the case the adhesive power of the resin fine particles (Q) and
the resin particles (P) in the composite resin particles is
increased, it is preferable to make the resin fine particles (Q)
and the resin particles (P) have mutually opposed positive and
negative electric charges at the time of dispersing them in a
water-based medium; to use those having opposed electric charge to
that of the resin fine particles (Q) and resin particles (P) among
the surfactant (S) or the water-soluble polymer (T) if the resin
fine particles (Q) and resin particles (P) have the same electric
charge; and to adjust the different of the SP value of the resin
(p) and the resin (q) to be 2 or lower. If the adhesive force is
high, it is generally preferable since the (TQ/TR) value becomes
high. Herein, (TQ/TR) means the ratio of the projected surface area
(TR) of the composite resin particles and the projected surface
area (TQ) of the resin fine particles (Q) and the projected surface
area is measured by photographing sample surface 10 times by an
electron microscope (magnification 30,000 times) and introducing
image information of the respective surface images into an image
analyzer though an interface.
The method for removing the water-based medium may be the following
methods [1] to [3] or combinations of these methods: [1] a method
of drying the water-based medium in reduced pressure or a normal
pressure; [2] a method of carrying out solid-liquid separation by a
centrifuge, a Supakura Filter, and/or a filter press and drying the
solid; and [3] a method of freezing the water-based dispersion and
drying the frozen dispersion (so-called freeze-drying method).
In the invention of the above-mentioned [1] and [2], commonly known
facilities such as a fluidized bed type drying apparatus, a vacuum
drying apparatus, and an air circulation drying apparatus may be
used as a drying apparatus.
If necessary, an air blowing classification apparatus or sieve may
be used for classification to obtain desired particle size
distribution.
The resin particles of the invention may be made to have smooth
particle surface or desired rough surface of the particles by
changing the particle diameter ratio (DVQ/DVP) of the resin fine
particles (Q) and the resin particles (P) and changing the depth of
the resin particles (P) in which the resin fine particles (Q) are
buried.
The depth of the resin particles (P) in which the resin fine
particles (Q) are buried may be controlled by as follows. [1] If
the resin fine particles (Q) and the resin particles (P) are made
to have mutually opposed positive and negative electric charges,
the depth of the resin particles (P) in which the resin fine
particles (Q) are buried becomes deep. In this case the respective
electric charges of the resin fine particles (Q) and the resin
particles (P) are higher, the depth tends to be deeper. [2] If the
resin fine particles (Q) and the resin particles (P) are made to
have electric charge with same polarity (both are positive or both
are negative), the (TQ/TR) of the resin fine particles (Q) becomes
lower and the depth tends to be shallow. In this case, generally if
the surfactant (S) and/or the water-soluble polymer (T)
[particularly having opposed electric charge to that of the resin
fine particles (Q) and the resin particles (P)] is used, (TQ/TR)
becomes high. In the case of the water-soluble polymer (T) is used,
the depth becomes shallower as the molecular weight of the
water-soluble polymer (T) is higher. [3] In the case the resin (p)
is a resin having an acidic functional group such as carboxyl,
phosphono group, or sulfo group (generally the molecular weight per
one acidic functional group is preferable to be 1,000 or lower),
the (TQ/TR) and the depth become high as the pH of the water-based
medium is lower. On the contrary, the (TQ/TR) and the depth become
small as the pH of the water-based medium is higher. [4] In the
case the resin (p) is a resin having a basic functional group such
as primary amino group, secondary amino group, tertiary amino
group, and quaternary ammonium group (generally the molecular
weight per one basic functional group is preferable to be 1,000 or
lower), the (TQ/TR) and the depth become high as the pH of the
water-based medium is higher. On the contrary, the (TQ/TR) and the
depth become small as the pH of the water-based medium is lower.
[5] The (TQ/TR) and the depth become high as the difference of the
SP values of the resin (p) and the resin (q) is made small.
In the case the powder fluidity of the resin particles is improved,
it is preferable that the BET specific surface area of the resin
particles is within a range from 0.5 to 5.0 m.sup.2/g.
The BET specific surface area may be measured by using a specific
surface meter (e.g. trade name: QUANTASORB, manufactured by Yuasa
Ionics Co., Ltd.) (measurement gas: He/Kr=99.9/0.1 vol. %,
calibration gas: nitrogen).
Similarly from a viewpoint of the powder fluidity, the centerline
average surface roughness (Ra) of the resin particles (P) is
preferably in a range from 0.01 to 0.8 .mu.m.
The (Ra) means the value calculated by mathematically averaging the
absolute values of the difference of the roughness curve and the
center line and can be measured by, for example, a scanning type
probe microscopic system (e.g. manufactured by Toyo Technica
Inc.).
EXAMPLES
Hereinafter the invention will be described more in detail, however
it is not intended that the invention be limited to the described
Examples.
The methods of measuring the properties of the polyester resins
obtained by Examples within the scope of the respective inventions
and Comparative Examples will be described below.
1. Hydroxy Value
A method standardized in JIS K 1557 (1970).
In the case there were solvent-insoluble fractions in samples due
to crosslinking, the samples were melted and kneaded by the
following method and used for measurement.
Kneader: LaboPlast Mill MODEL 30R150, manufactured by Toyo Seiki
Seisaku-Sho Ltd.
Kneading conditions: at 130.degree. C. and 70 rpm for 30
minutes
2. Acid Value
A method standardized in JIS K 0070 (1992).
In the case there were solvent-insoluble fractions in samples due
to crosslinking, the samples were melted and kneaded by the same
method as that in the case of the hydroxy value and used for
measurement.
3. Softening Point (Hereinafter, Referred Also to as Tm)
By the softening point measurement method as described in the
second invention.
Examples Relevant to the First to the Third Inventions
Examples 1 to 4, Comparative Examples 1 to 4
Example 1
[Synthesis of Linear Polyester]
To a reaction tank equipped with a cooling tube, a stirrer, and a
nitrogen introduction tube, 1,2-propylene glycol (hereinafter,
simply referred to as propylene glycol) 639 part (24.5 mole),
bisphenol A-2 mole EO adduct 180 part (1.6 mole), terephthalic acid
dimethyl ester 653 part (9.8 mole), adipic acid 10 part (0.2 mole),
and as a condensation catalyst, tetrabutoxy titanate 3 part were
loaded and under nitrogen gas stream, reaction was carried out at
180.degree. C. for 8 hours while the produced methanol was removed.
Successively, while the reaction system was gradually heated to
230.degree. C. and the produced propylene glycol and water were
removed under nitrogen gas stream, reaction was carried out for 4
hours and further continued at a pressure reduced to 5 to 20 mmHg
and the product was discharged when the softening point reached
90.degree. C. The recovered propylene glycol was 263 part (10.1
mole). After cooled to a room temperature, the discharged resin was
pulverized for granulation. The obtained product was linear
polyester (Aa-1).
The linear polyester (Aa-1) had 1500 of Mn, 2500 of Mp, 3.0% of the
content of components with 500 or lower molecular weight, 0% of the
THF-insoluble fractions, 82 kJ of the molar average cohesive energy
of the polyol component (hereinafter abbreviated as En), 300 of a
storage modulus at 150.degree. C. (hereinafter abbreviated as G'),
90.degree. C. of Tm, 5 to 11 of a loss tangent at 130 to
200.degree. C. (hereinafter abbreviated as tan .delta.) (in the
temperature range exceeding 150.degree. C., since the measurement
was impossible because of too low elasticity, the value at a
temperature in a range from 130 to 150.degree. C. was employed. It
is same for the following respective linear polyesters unless
otherwise specified).
The number of the mole in each parenthesis is written for showing
the relative mole ratio of the respective starting materials (same
as the following examples).
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 614
part (23.8 mole), bisphenol A-2 mole EO adduct 156 part (1.4 mole),
terephthalic acid dimethyl ester 627 part (9.5 mole), adipic acid
25 part (0.5 mole), and tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 180.degree.
C. for 8 hours while the produced methanol was removed.
Successively, while the reaction system was gradually heated to
230.degree. C. and the produced propylene glycol and water were
removed under nitrogen gas stream, reaction was carried out for 4
hours and further continued for 1 hour at a pressure reduced to 5
to 20 mmHg. The recovered propylene glycol was 288 part (11.2
mole). After cooled to 180.degree. C., trimellitic anhydride 98
part (1.5 mole) was added and the reaction was carried out for 2
hours in closed condition at a normal pressure and continued at
220.degree. C. and a normal pressure and when the softening point
reached 180.degree. C., the product was discharged and cooled to a
room temperature and pulverized for granulation. The obtained
product was non-linear polyester (Ab-1).
The non-linear polyester (Ab-1) had 4000 of Mn, 8000 of Mp, 1.3% of
the content of components with 500 or lower molecular weight, 30%
of the THF-insoluble fractions, 82 kJ of En, 3.6.times.10.sup.5 of
G', 180.degree. C. of Tm, and 1.2 to 2.0 of tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-1) 600 part and the non-linear polyester
(Ab-1) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (1) for a toner of the
invention.
The polyester resin (1) for a toner had Tg of 64.degree. C., 2200
of Mn, 3200 of Mp, 2.3% of the components with 500 or lower
molecular weight, and 13% of the THF-insoluble fractions.
Example 2
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
720 part (23.8 mole), terephthalic acid dimethyl ester 735 part
(9.8 mole), adipic acid 29 part (0.5 mole), and tetrabutoxy
titanate 3 part were loaded and reaction was carried out in the
same manner as that for the linear polyester (Aa-1) of Example 1
and the product was discharged when the softening point reached
94.degree. C. The recovered propyleneglycol was 235 part (7.8
mole). After cooled to a room temperature, the discharged resin was
pulverized for granulation. The obtained product was linear
polyester (Aa-2).
The linear polyester (Aa-2) had 2700 of Mn, 5800 of Mp, 2.0% of the
content of components with 500 or lower molecular weight, 0% of the
THF-insoluble fractions, 73 kJ of En, 300 of G', Tm of 90.degree.
C., 5 to 11 of tan .delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 663
part (22.5 mole), terephthalic acid dimethyl ester 677 part (9.0
mole), adipic acid 57 part (1.0 mole), and tetrabutoxy titanate 3
part were loaded and reaction was carried out in the same manner as
that for the non-linear polyester (Ab-1) of Example 1. The
recovered propylene glycol was 251 part (8.5 mole). After cooled to
180.degree. C., trimellitic anhydride 112 part (1.5 mole) was added
and reaction was carried out in the same manner as that for the
linear polyester (Ab-1) and when the softening point reached
180.degree. C., the product was discharged and cooled to a room
temperature and pulverized for granulation. The obtained product
was non-linear polyester (Ab-2).
The non-linear polyester (Ab-2) had 3900 of Mn, 8000 of Mp, 1.3% of
the content of components with 500 or lower molecular weight, 29%
of the THF-insoluble fractions, 73 kJ of En, 3.6.times.10.sup.5 of
G', Tm of 180.degree. C., and 1.2 to 2.1 of tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-2) 600 part and the non-linear polyester
(Ab-2) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (2) for a toner of the
invention.
The polyester resin (2) for a toner had Tg of 64.degree. C., 3200
of Mn, 6700 of Mp, 1.6% of the components with 500 or lower
molecular weight, and 13% of the THF-insoluble fractions.
Example 3
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
701 part (18.8 mole), terephthalic acid dimethyl ester 716 part
(7.5 mole), adipic acid 180 part (2.5 mole), and tetrabutoxy
titanate 3 part were loaded and reaction was carried out in the
same manner as that for the linear polyester (Aa-1) of Example 1
and the product was discharged when the softening point reached
150.degree. C. The recovered propylene glycol was 316 part (8.5
mole). After cooled to a room temperature, the discharged resin was
pulverized for granulation. The obtained product was linear
polyester (Aa-3).
The linear polyester (Aa-3) had 8000 of Mn, 20000 of Mp, 1.6% of
the content of components with 500 or lower molecular weight, 0% of
the THF-insoluble fractions, 73 kJ of En, 1.6.times.10.sup.6 of G',
Tm of 150.degree. C., 5 to 11 of tan .delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 557
part (17.5 mole), terephthalic acid dimethyl ester 569 part (7.0
mole), adipic acid 184 part (3.0 mole), and tetrabutoxy titanate 3
part were loaded and reaction was carried out in the same manner as
that for the non-linear polyester (Ab-1) of Example 1. The
recovered propylene glycol was 175 part (5.5 mole). After cooled to
180.degree. C., trimellitic anhydride 121 part (1.5 mole) was added
and reaction was carried out in the same manner as that for the
linear polyester (Ab-1) and when the softening point reached
180.degree. C., the product was discharged and cooled to a room
temperature and pulverized for granulation. The obtained product
was non-linear polyester (Ab-3).
The non-linear polyester (Ab-3) had 8500 of Mn, 23000 of Mp, 0.9%
of the content of components with 500 or lower molecular weight,
30% of the THF-insoluble fractions, 73 kJ of En, 3.6.times.10.sup.5
of G', Tm of 180.degree. C., and 1.2 to 1.9 of tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-3) 600 part and the non-linear polyester
(Ab-3) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (3) for a toner of the
invention.
The polyester resin (3) for a toner had Tg of 62.degree. C., 8100
of Mn, 22000 of Mp, 1.3% of the components with 500 or lower
molecular weight, and 13% of the THF-insoluble fractions.
Example 4
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
540 part (25.0 mole), bisphenol A-2 mole EO adduct 372 part (4.0
mole), terephthalic acid dimethyl ester 551 part (10.0 mole), and
tetrabutoxy titanate 3 part were loaded and under nitrogen gas
stream, reaction was carried out at 180.degree. C. for 8 hours
while the produced methanol was removed. Successively, while the
reaction system was gradually heated to 230.degree. C. and the
produced propylene glycol and water were removed under nitrogen gas
stream, reaction was carried out for 4 hours and further continued
at a pressure reduced to 5 to 20 mmHg and the product was
discharged when the softening point reached 94.degree. C. The
recovered propylene glycol was 281 part (13.0 mole). After cooled
to a room temperature, the discharged resin was pulverized for
granulation. The obtained product was linear polyester (Aa-4).
The linear polyester (Aa-4) had 2700 of Mn, 5800 of Mp, 2.5% of the
content of components with 500 or lower molecular weight, 0% of the
THF-insoluble fractions, 96 kJ of En, 300 of G', Tm of 94.degree.
C., 5 to 11 of tan .delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 531
part (24.3 mole), bisphenol A-2 mole EO adduct 330 part (3.5 mole),
terephthalic acid dimethyl ester 542 part (9.7 mole), adipic acid
13 part (0.3 mole), and tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 180.degree.
C. for 8 hours while the produced methanol was removed.
Successively, while the reaction system was gradually heated to
230.degree. C. and the produced propylene glycol and water were
removed under nitrogen gas stream, reaction was carried out for 4
hours and further continued for 1 hour at a pressure reduced to 5
to 20 mmHg. The recovered propylene glycol was 301 part (13.8
mole). After cooled to 180.degree. C., trimellitic anhydride 83
part (1.5 mole) was added and the reaction was carried out for 2
hours in closed condition at a normal pressure and continued at
220.degree. C. at a normal pressure and when the softening point
reached 180.degree. C., the product was discharged and cooled to a
room temperature and pulverized for granulation. The obtained
product was non-linear polyester (Ab-4).
The non-linear polyester (Ab-4) had 4000 of Mn, 8000 of Mp, 1.3% of
the content of components with 500 or lower molecular weight, 31%
of the THF-insoluble fractions, 96 kJ of En, 3.6.times.10.sup.5 of
G', 180.degree. C. of Tm, and 1.1 to 1.4 of tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-4) 600 part and the non-linear polyester
(Ab-4) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (4) for a toner of the
invention.
The polyester resin (4) for a toner had Tg of 63.degree. C., 3200
of Mn, 6700 of Mp, 1.9% of the components with 500 or lower
molecular weight, and 14% of the THF-insoluble fractions.
Comparative Example 1
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
PO adduct 466 part (9.0 mole), bisphenol A-2 mole EO adduct 341
part (7.0 mole), terephthalic acid 247 part (10.0 mole), and
tetrabutoxy titanate 3 part were loaded and under nitrogen gas
stream, reaction was carried out at 230.degree. C. for 5 hours
while the produced water was removed. Successively, reaction was
carried out under a pressure reduced to 5 to 20 mmHg and when the
acid value reached 2, the reaction system was cooled to 180.degree.
C. and trimellitic anhydride 74 part (2.6 mole) was added and the
product was discharged after reaction for 2 hours in closed
condition at a normal temperature. After cooled to a room
temperature, the discharged resin was pulverized for granulation.
The obtained product was linear polyester (Aa'-5).
The linear polyester (Aa'-5) had 1500 of Mn, 2500 of Mp, 4.2% of
the content of components with 500 or lower molecular weight, 0% of
the THF-insoluble fractions, 166 kJ of En, 300 of G', Tm of
90.degree. C., 5 to 11 of tan .delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, bisphenol A-3 mole PO
adduct 679 part (10.8 mole), phenol novolak EO adduct 47 part (0.37
mole), terephthalic acid 260 part (10.0 mole), and tetrabutoxy
titanate 3 part were loaded and under nitrogen gas stream, reaction
was carried out at 230.degree. C. for 7 hours while the produced
water was removed. Successively, reaction was carried out under a
pressure reduced to 5 to 20 mmHg and when the acid value reached 2
or lower, the reaction system was cooled to 180.degree. C. and
trimellitic anhydride 87 part (2.9 mole) was added and the product
was discharged after reaction for 2 hours in closed condition at a
normal temperature. After cooled to a room temperature, the
discharged resin was pulverized for granulation. The obtained
product was non-linear polyester (Ab'-5).
The non-linear polyester (Ab'-5) had 4200 of Mn, 7400 of Mp, 3.2%
of the content of components with 500 or lower molecular weight,
42% of the THF-insoluble fractions, 184 kJ of En,
5.0.times.10.sup.5 of G', 94.degree. C. of Tm, and 0.3 to 0.7 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-5) 600 part and the non-linear polyester
(Ab'-5) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (1) for a toner for
comparison.
The polyester resin (1) for a toner for comparison had Tg of
64.degree. C., 2600 of Mn, 4500 of Mp, 3.8% of the components with
500 or lower molecular weight, and 16% of the THF-insoluble
fractions.
Comparative Example 2
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
PO adduct 404 part (7.0 mole), bisphenol A-2 mole EO adduct 380
part (7.0 mole), terephthalic acid 276 part (10.0 mole), and
tetrabutoxy titanate 3 part were loaded and under nitrogen gas
stream, reaction was carried out at 230.degree. C. for 5 hours
while the produced water was removed. Successively, reaction was
carried out under a pressure reduced to 5 to 20 mmHg and when the
acid value reached 2 or lower, the reaction system was cooled to
180.degree. C. and trimellitic anhydride 74 part (2.3 mole) was
added and the product was discharged after reaction for 2 hours in
closed condition at a normal temperature and after cooled to a room
temperature, the discharged resin was pulverized for granulation.
The obtained product was linear polyester (Aa'-6).
The linear polyester (Aa'-6) had 1900 of Mn, 4200 of Mp, 4.0% of
the content of components with 500 or lower molecular weight, 0% of
the THF-insoluble fractions, 90 kJ of En, 300 of G', Tm of
90.degree. C., 5 to 11 of tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-6) 600 part and the non-linear polyester
(Ab'-5) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (2) for a toner for
comparison.
The polyester resin (2) for a toner for comparison had Tg of
64.degree. C., 2800 of Mn, 5500 of Mp, 3.7% of the components with
500 or lower molecular weight, and 17% of the THF-insoluble
fractions.
Comparative Example 3
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
692 part (25.0 mole), terephthalic acid dimethyl ester 707 part
(10.0 mole), and as a condensation catalyst, tetrabutoxy titanate 3
part were loaded and under nitrogen gas stream, reaction was
carried out at 180.degree. C. for 8 hours while the produced
methanol was removed. Successively, while the temperature was
increased gradually to 230.degree. C. and produced propylene glycol
and water were removed under nitrogen gas stream, reaction was
carried for 4 hours and further continues for 1 hour under a
pressure reduced to 5 to 20 mmHg and the product was discharged.
The recovered propylene glycol was 166 part (6.0 mole). There
after, the product was cooled to a room temperature however the
product was not turned to be a resin but like a paste. The obtained
product was named as a linear polyester (Aa'-7).
The linear polyester (Aa'-7) had 800 of Mn, 1200 of Mp, 0% of the
THF-insoluble fractions. Since the polyester (Aa'-7) was not turned
to be a resin, it was not used for toner production.
Comparative Example 4
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
EO adduct 722 part (10.3 mole), terephthalic acid 356 part (10.0
mole), and as a condensation catalyst, tetrabutoxy titanate 3 part
were loaded and under nitrogen gas stream, reaction was carried out
at 230.degree. C. for 5 hours while the produced water was removed.
Successively, reaction was carried under a pressure reduced to 5 to
20 mmHg and when the acid value reached 2 or lower, the reaction
system was cooled to 180.degree. C. and trimellitic anhydride 25
part (0.6 mole) was added and after 2 hour reaction in closed state
at a normal pressure, the product was discharged, cooled to a room
temperature, and pulverized for granulation. The obtained product
was named as a linear polyester (Aa'-8).
The linear polyester (Aa'-8) had 7000 of Mn, 19000 of Mp, 3.3% of
the components with 500 or lower molecular weight, 0% of the
THF-insoluble fractions, 164 kJ of En, 1.0.times.10.sup.5 of G',
140.degree. C. of Tm, 0.8 to 4 of tan .delta. at 130 to 200.degree.
C.
[Synthesis of Non-linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-3 mole
PO adduct 693 part (10.8 mole), phenol novolak EO adduct 48 part
(0.37 mole), terephthalic acid 239 part (9.0 mole), and as a
condensation catalyst, tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 230.degree.
C. for 7 hours while the produced water was removed. Successively,
reaction was carried out under a pressure reduced to 5 to 20 mmHg
and when the acid value reached 2 or lower, the reaction system was
cooled to 180.degree. C. and trimellitic anhydride 89 part (2.9
mole) was added and after reaction for 2 hours in closed condition
at a normal temperature, and continued at 220.degree. C. at normal
pressure and when the softening point reached 180.degree. C., the
product was discharged, cooled to a room temperature, and
pulverized for granulation. The obtained product was named as
non-linear polyester (Ab'-8).
The non-linear polyester (Ab'-8) had 8800 of Mn, 22000 of Mp, 3.3%
of the content of components with 500 or lower molecular weight,
42% of the THF-insoluble fractions, 184 kJ of En,
5.0.times.10.sup.5 of G', Tm of 180.degree. C., and 0.3 to 0.7 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-8) 600 part and the non-linear polyester
(Ab'-8) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (4) for a toner for
comparison.
The polyester resin (4) for a toner for comparison had 63.degree.
C. of Tg, 8000 of Mn, 21000 of Mp, 3.3% of the components with 500
or lower molecular weight, and 16% of the THF-insoluble
fractions.
Examples (1) to (4) and Comparative Example (1), (2), and (4)
Carbon black MA-100 (manufactured by Mitsubishi Chemical Corp.) 8
part, carnauba wax 5 part, a charge control agent T-77
(manufactured by Hodogaya Chemical Co., Ltd.) 1 part were added to
respective polyester resins for a toner (1) to (4) within the scope
of the invention and polyester resins for a toner for comparison
(1)-(2), (4) and toners produced by the following method.
At first, each mixture was preliminarily mixed by a Henshel mixer
(FM10B, manufactured by Mitsui Miike Chemical Plant Service Inc.)
and then kneaded by a twin-screw extruder (PCM-30, manufactured by
Ikegai Co., Ltd.). Successively, each mixture was finely pulverized
by ultrasonic jet pulverizer Labo-Jet (manufactured by Nippon
Pneumatic Industry Co., Ltd.) and classified by an air current
classifier (MDS-I, manufactured by Nippon Pneumatic Industry Co.,
Ltd.) to obtain toner particles with 8 .mu.m of particle diameter
D50. Next, colloidal silica (Aerosil R972: manufactured by Nippon
Aerosil Co., Ltd.) 0.5 part was added to each obtained toner
particles 100 part and mixed by a sample mill to obtain toners (1)
to (4) within a scope of the invention and toners (1), (2), and (4)
for comparison.
The toners were evaluated by the following evaluation methods and
the evaluation results are shown in Table 1.
TABLE-US-00001 TABLE 1 Grindability MFT Gross HOT average particle
Toner No. (.degree. C.) (.degree. C.) (.degree. C.) Fluidity
diameter (.mu.m) Toner (1) 125 145 230 .largecircle. 11 Toner (2)
120 140 230 .largecircle. 11 Toner (3) 125 145 230 .largecircle. 12
Toner (4) 130 145 230 .largecircle. 11 Toner for 135 165 215
.DELTA.X 12 comparison (1) Toner for 130 165 230 .DELTA.X 12
comparison (2) Toner for 130 175 230 .DELTA. 16 comparison (4)
[Evaluation Methods] [1] Minimum fixing temperature (MFT)
Un-fixed images developed by a commercialized copying machine (AR
5030: manufactured by SHARP CORP.) were subjected to evaluation by
using a fixing apparatus of a commercialized copying machine (AR
5030: manufactured by SHARP CORP.). The fixing roll temperature at
which the remaining ratio of the image density became 70% or higher
after fixed images were scratched with a pat was defined as the
minimum fixing temperature. [2] Hot offset occurrence temperature
(HOT)
The fixing was evaluated in the same manner as described above for
MFT and occurrence of the hot offset in the fixed images was
observed by eye observation. The fixing roll temperature at which
the offset took place was defined as the hot offset occurrence
temperature. [3] Gross development temperature
In the same manner as described above for MFT, the developed
un-fixed images were subjected to fixing evaluation by using a
fixing apparatus of a commercialized copying machine (LBP2160:
manufactured by CANON INC.). The fixing roll temperature at which
the 60.degree. gross of the fixed images became 10% or higher was
defined as the gross development temperature. [4] Toner
fluidity
The static bulk density of each toner was measured by a powder
tester (manufactured by Hosokawa Micron Co., Ltd.) and the toner
fluidity was determined according to the following criteria. Toners
marked with .DELTA. or higher were regarded as practically usable.
Static bulk density (g/100 ml): toner fluidity
TABLE-US-00002 36 or higher: .largecircle. 33 to less than 36:
.largecircle..DELTA. 30 to less than 33: .DELTA. 27 to less than
30: .DELTA.X less than 27: X
[5] Grindability
Respective coarsely pulverized toners (passing 8.6 mesh and on 30
mesh) which were kneaded by a biaxial kneader and cooled were
finely pulverized by ultrasonic jet pulverizer Labo-Jet
(manufactured by Nippon Pneumatic Industry Co., Ltd.) under the
following conditions: Grinding pressure: 0.5 MPa Adjuster ring: 15
mm Size of louvers: intermediate Pulverizing time: 10 minutes
Without being classified, the pulverized products were subjected to
measurement of volume average particle diameter by Coulter Counter
AT II (manufactured by US Coulter Electronics Corp.) to measure the
grindability. In this measurement method, if the volume average
particle diameter is 12 .mu.m or smaller, the grindability can be
said to be good.
Examples 11 and 12 and Comparative Examples 11 to 13
Example 11
[Synthesis of Non-linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
817 part (22.6 mole), terephthalic acid dimethyl ester 831 part
(9.0 mole), adipic acid 70 part (1.0 mole), and as a condensation
catalyst tetrabutoxy titanate 3 part were loaded and under nitrogen
gas stream, reaction was carried out at 180.degree. C. for 8 hours
while the produced methanol was removed. Successively, while the
reaction system was gradually heated to 230.degree. C. and the
produced propylene glycol and water were removed under nitrogen gas
stream, reaction was carried out for 4 hours and further continued
for 1 hour at a pressure reduced to 5 to 20 mmHg. When the
softening point reached 85.degree. C., the product was cooled to
180.degree. C. and trimellitic anhydride 37 part (0.4 mole) was
added and the reaction was carried out for 2 hours in closed
condition at a normal pressure and continued at 220.degree. C. and
a normal pressure and when the softening point reached 160.degree.
C., the product was discharged. The recovered propyleneglycol
accordingly was 450 part (12 mole). After cooled to a room
temperature, the resulting discharged resin was pulverized for
granulation. The obtained product was non-linear polyester
(Ab-11).
The non-linear polyester (Ab-11) had Tg of 60.degree. C., 5800 of
Mn, 10000 of peak top molecular weight, 3% of the THF-insoluble
fractions, 73 kJ of En, 1.6.times.10.sup.5 of G', 160.degree. C. of
Tm, and 1.2 to 2.5 of tan .delta..
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, 1,2-propylene
glycol 782 part (22.7 mole), terephthalic acid dimethyl ester 834
part (9.5 mole), adipic acid 33 part (0.5 mole), and as a
condensation catalyst, tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 180.degree.
C. for 8 hours while the produced methanol was removed.
Successively, while the reaction system was gradually heated to
230.degree. C. and the produced propylene glycol and water were
removed under nitrogen gas stream, reaction was carried out for 4
hours and further continued at a pressure reduced to 5 to 20 mmHg
and the reaction system was cooled when the softening point reacted
at 95.degree. C. The recovered propyleneglycol accordingly was 380
part (11 mole). When the temperature became 180.degree. C.,
trimellitic anhydride 17 part was added and the reaction system was
kept at 180.degree. C. for 1.5 hours and then the obtained product
was discharged. After cooled to a room temperature, the resulting
discharged resin was pulverized for granulation. The obtained
product was linear polyester (Aa-11).
The linear polyester (Aa-11) had Tg of 60.degree. C., 2800 of Mn,
5800 of peak top molecular weight, 73 kJ of En, 140 of G',
100.degree. C. of Tm, and 4 to 20 of tan .delta..
[Production of Polyester Resin for Toner]
The non-linear polyester (Ab-11) 400 part and the linear polyester
(Aa-11) 600 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (11) for a toner of the
invention.
Example 12
[Synthesis of Non-linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
391 part (22.3 mole), terephthalic acid dimethyl ester 358 part
(8.0 mole), adipic acid 67 part (2.0 mole), and as a condensation
catalyst, tetrabutoxy titanate 3 part were loaded and under
nitrogen gas stream, reaction was carried out at 180.degree. C. for
8 hours while the produced methanol was removed. Successively,
while the reaction system was gradually heated to 230.degree. C.
and the produced propylene glycol and water were removed under
nitrogen gas stream, reaction was carried out for 4 hours. Next,
bisphenol A-2 mole propylene oxide adduct 561 part (7 mole), phenol
novolak resin (5.6 nuclear bodies)-ethylene oxide adduct 56 part
(0.3 mole) were further loaded and reaction was carried out at
230.degree. C. and a normal pressure for 4 hours and then continued
at a pressure reduced to 5 to 20 mmHg. When the softening point
reached 90.degree. C., the reaction system was cooled. When it was
cooled to 180.degree. C. and trimellitic anhydride 20 part (0.45
mole) was added and the reaction system was kept at 180.degree. C.
for 1.5 hours and heated to 220.degree. C. The pressure was reduced
properly by 5 to 20 mmHg and when the softening point reached
135.degree. C., the product was discharged. The recovered propylene
glycol accordingly was 314 part (17.5 mole). After cooled to a room
temperature, the resulting discharged resin was pulverized for
granulation. The obtained product was non-linear polyester
(Ab-12).
The non-linear polyester (Ab-12) had TG of 60.degree. C., 4200 of
Mn, 7800 of peak top molecular weight, 3% of the THF-insoluble
fractions, 97 kJ of En, 1.36.times.10.sup.4 of G', 135.degree. C.
of Tm, and 1.2 to 1.9 of tan .delta..
[Polyester Resin for a Toner]
The non-linear polyester (Ab-12) synthesized in the above-mentioned
manner was used as a polyester resin for a toner (12).
Comparative Example 11
[Synthesis of Non-linear Polyester]
To a reaction tank equipped with a cooling tube, a stirrer, and a
nitrogen introduction tube, bisphenol A-2 mole propylene oxide
adduct 552 part (2.5 mole), bisphenol A-2 mole ethylene oxide
adduct 184 part (8 mole), terephthalic acid 287 part (8.2 mole),
and dibutyltin oxide 3 part were loaded and under nitrogen gas
stream, dehydration esterification was carried out at 230.degree.
C. At the time when no water was discharged, the pressure was
reduced and esterification was promoted until the acid value
reached 1.0. After that, the temperature was adjusted to be
220.degree. C. and trimellitic anhydride 49 part (1.2 mole) was
added and the temperature was kept as it was for 1 hour. After
that, reaction was carried out at a proper pressure reduced by 5 to
20 mmHg and when the softening temperature reached 115.degree. C.,
the product was discharged out of the reaction tank to obtain
non-linear polyester (Ab'-13). The non-linear polyester (Ab'-13)
had Tg of 60.degree. C., 3200 of Mn, 5800 of peak top molecular
weight, 0% of the THF-insoluble fractions, 165 kJ of En,
5.8.times.10.sup.3 of G', Tm of 115.degree. C., and 1.1 to 5.2 of
tan .delta..
[Polyester Resin for a Toner]
The non-linear polyester (Ab'-13) synthesized in the
above-mentioned manner was used as a polyester resin for a toner
(11) for comparison.
Comparative Example 12
[Synthesis of Non-linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
propylene oxide adduct 138 part (2.2 mole), bisphenol A-2 mole
ethylene oxide adduct 616 part (8.5 mole), terephthalic acid 224
part (7.5 mole), and as a condensation catalyst, dibutyltin oxide 3
part were loaded and under nitrogen gas stream, reaction was
carried out at 230.degree. C. for 7 hours while produced water was
removed. Next, the reaction was carried out under a reduced
pressure of 5 to 20 mmHg and when the acid value became 1, the
reaction system was cooled to 180.degree. C. and trimellitic acid
87 part (2.5 mole) was added and after 2 hour reaction in closed
state at a normal pressure, the reaction was carried out at
220.degree. C. at a normal pressure and then at a reduced pressure
of 5 to 20 mmHg and when the softening temperature reached
185.degree. C., the product was discharged, cooled to a room
temperature, and pulverized for granulation. The obtained product
was a non-linear polyester (Ab'-14).
The non-linear polyester (Ab'-14) had 6000 of Mn, 10000 of Mp, 183
kJ of En, 5.0.times.10.sup.5 of G', Tm of 185.degree. C., and 0.1
to 0.4 of tan .delta..
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
propylene oxide adduct 552 part (10.0 mole), bisphenol A-2 mole
ethylene oxide adduct 208 part (4.0 mole), terephthalic acid 263
part (10.0 mole), and as a condensation catalyst, dibutyltin oxide
3 part were loaded and under nitrogen gas stream, reaction was
carried out at 230.degree. C. for 5 hours while the produced water
was removed. Next, when the acid value became 1.5, the reaction
system was cooled to 180.degree. C. and trimellitic acid 34 part
was added and after 2 hour reaction in closed state at a normal
pressure, the product was discharged, cooled to a room temperature,
and pulverized for granulation. The obtained product was a linear
polyester (Aa'-14).
The linear polyester (Aa'-14) had 2800 of Mn, 5200 of Mp, 166 kJ of
En, 1.4.times.10.sup.2 of G', Tm of 100.degree. C., and 3 to 15 of
tan .delta..
[Production of Polyester Resin for Toner]
The non-linear polyester (Ab'-14) 400 part and the linear polyester
(Aa'-14) 600 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (12) for a toner for
comparison.
Comparative Example 13
[Synthesis of Non-linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
propylene oxide adduct 137 part (2.2 mole), bisphenol A-2 mole
ethylene oxide adduct 612 part (8.5 mole), terephthalic acid 267
part (9.0 mole), and as a condensation catalyst, dibutyltin oxide 3
part were loaded and under nitrogen gas stream, reaction was
carried out at 230.degree. C. for 7 hours while produced water was
removed. Next, the reaction was carried out under a reduced
pressure of 5 to 20 mmHg and when the acid value became 1, the
reaction system was cooled to 180.degree. C. and trimellitic acid
52 part (1.5 mole) was added and after 2 hour reaction in closed
state at a normal pressure, the reaction was carried out at
220.degree. C. and a normal pressure and properly at a reduced
pressure of 5 to 20 mmHg and when the softening temperature reached
160.degree. C., the product was discharged, cooled to a room
temperature, and pulverized for granulation. The obtained product
was a non-linear polyester (Ab'-15).
The non-linear polyester (Ab'-15) had 11000 of Mn, 240000 of Mp,
183 kJ of En, 2.4.times.10.sup.5 of G', Tm of 160.degree. C., and
0.5 to 0.9 of tan .delta..
[Production of Polyester Resin for Toner]
The non-linear polyester (Ab'-15) 400 part and the linear polyester
(Aa'-15) 600 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (13) for a toner for
comparison.
Examples (11) and (12) and Comparative Example (11) to (13)
Cyanine Blue KRO (manufactured by Sanyo Color Works Ltd.) 8 part
and carnauba wax 5 part were added to 100 part of respective
polyester resins for a toner (11) and (12) within the scope of the
invention and polyester resins for a toner for comparison (11) to
(13) and toners were produced by the following method.
At first, each mixture was preliminarily mixed by a Henshel mixer
(FM10B, manufactured by Mitsui Miike Chemical Plant Service Inc.)
and then kneaded by a biaxial kneader (PCM-30, manufactured by
Ikegai Co., Ltd.). Successively, each mixture was finely pulverized
by ultrasonic jet pulverizer Labo-Jet (manufactured by Nippon
Pneumatic Industry Co., Ltd.) and classified by an air current
classifier (MDS-I, manufactured by Nippon Pneumatic Industry Co.,
Ltd.) to obtain toner particles with 8 .mu.m of particle diameter
D50. Next, colloidal silica (Aerosil R972: manufactured by Nippon
Aerosil Co., Ltd.) 0.5 part was added to each obtained toner
particles 100 part and mixed by a sample mill to obtain toners (11)
and (12) within a scope of the invention and toners (11) to (13)
for comparison.
The toners were evaluated by the above-mentioned evaluation methods
and the evaluation results are shown in Table 2.
TABLE-US-00003 TABLE 2 Grindability MFT Gross HOT average particle
Toner No. (.degree. C.) (.degree. C.) (.degree. C.) Fluidity
diameter (.mu.m) Toner (11) 125 145 230 .largecircle. 11 or higher
Toner (12) 125 145 220 .largecircle. 11 Toner for 130 145 170
.DELTA.X 11 comparison (11) Toner for 145 180 230 .DELTA.X 15
comparison (12) or higher Toner for 125 180 230 .DELTA. 13
comparison (13) or higher
Examples 21 to 24 and Comparative Examples 21 and 22
Example 21
To the reaction tank same as that of Example 1, propylene glycol
127 part, terephthalic acid dimethyl ester 454 part, adipic acid
38, bisphenol A-2 mole propylene oxide adduct 452 part, phenol
novolak resin (average polymerization degree 5.6)-EO adduct 2.3
part, and as a condensation catalyst, tetrabutoxy titanate 3 part
were loaded and under nitrogen gas stream, reaction was carried out
at 180.degree. C. for 12 hours while the produced methanol was
removed. Successively, while the reaction system was gradually
heated to 230.degree. C. and the produced water was removed under
nitrogen gas stream, reaction was carried out for 4 hours and
further continued at a pressure reduced to 5 to 20 mmHg and when
the softening point reached 98.degree. C., the product was cooled.
When the temperature reached 180.degree. C., trimellitic anhydride
17 part was added and the reaction was carried out for 1 hour under
stirring condition and the product was discharged. The discharged
polyester resin [21] had 3600 of Mn, 8000 of Mp, Tg of 60.degree.
C., 114 kJ of En, 140 of G', Tm of 102.degree. C., and 6 to 11 of
tan .delta..
Example 22
To the reaction tank same as that of Example 1, propylene glycol
347 part, terephthalic acid dimethyl ester 317 part, adipic acid
60, and as a condensation catalyst, tetrabutoxy titanate 3 part
were loaded and under nitrogen gas stream, reaction was carried out
at 180.degree. C. for 8 hours while the produced methanol was
removed. Successively, bisphenol A-2 mole propylene oxide adduct
596 part, phenol novolak resin (average polymerization degree
5.6)-EO adduct 2.3 part were added and while the reaction system
was gradually heated to 230.degree. C. and the produced propylene
glycol and water were removed under nitrogen gas stream, reaction
was carried out for 4 hours and further continued at a pressure
reduced to 5 to 20 mmHg and when the softening point reached
98.degree. C., the product was cooled. The recovered propylene
glycol was 295 part. When the temperature reached 180.degree. C.,
trimellitic anhydride 17 part was added and the reaction was
carried out for 1 hour under stirring condition and the product was
discharged. The discharged polyester resin [22] had 3700 of Mn,
7900 of Mp, Tg of 60.degree. C., 140 kJ of En, 150 of G',
102.degree. C. of Tm, and 5 to 11 of tan .delta..
Example 23
To the reaction tank same as that of Example 1, propylene glycol
380 part, phenol novolak resin (average polymerization degree
5.6)-EO adduct 46 part, terephthalic acid dimethyl ester 351 part,
adipic acid 28, and as a condensation catalyst, tetrabutoxy
titanate 3 part were loaded and under nitrogen gas stream, reaction
was carried out at 180.degree. C. for 8 hours while the produced
methanol was removed. Successively, while the reaction system was
gradually heated to 230.degree. C. and the produced propylene
glycol and water were removed under nitrogen gas stream, reaction
was carried out for 4 hours and further continued at a pressure
reduced to 5 to 20 mmHg and when the softening point reached
141.degree. C., the product was discharged. The recovered propylene
glycol was 190 part. The discharged polyester resin [23] had 3700
of Mn, 11000 of Mp, Tg of 65.degree. C., 73 kJ of En,
8.7.times.10.sup.3 of G', Tm of 142.degree. C., and 1.6 to 1.8 of
tan .delta..
Comparative Example 21
To the reaction tank same as that of Example 1, terephthalic acid
ethylene glycol diester 453 part, adipic acid 36, and as a
condensation catalyst, dibutyltin oxide 3 part were loaded and
bisphenol A-2 mole propylene oxide adduct 596 part and trimellitic
anhydride 0.9 part were added and while the reaction system was
gradually heated to 230.degree. C. and the produced ethylene glycol
and water were removed under nitrogen gas stream, reaction was
carried out for 7 hours and further continued at a pressure reduced
to 1 to 20 mmHg and when the softening point reached 98.degree. C.,
the product was cooled. The recovered ethylene glycol was 239 part.
When the temperature reached 180.degree. C., trimellitic anhydride
17 part was added and the reaction was carried out for 1 hour under
stirring condition and the product was discharged. The discharged
polyester resin [2'] for comparison had 4200 of Mn, 8100 of Mp, Tg
of 58.degree. C., 167 kJ of En, 140 of G', Tm of 101.degree. C.,
and 4 to 11 of tan .delta..
Example 24 and Comparative Example 22
Cyanine Blue KRO (manufactured by Sanyo Color Works Ltd.) 8 part
and carnauba wax 5 part were added to 100 part of respective
polyester resins [21] to [23] within the scope of the invention and
polyester resin [21'] for comparison and toners were produced by
the following method.
At first, each mixture was preliminarily mixed by a Henshel mixer
(FM10B, manufactured by Mitsui Miike Chemical Plant Service Inc.)
and then kneaded by a biaxial kneader (PCM-30, manufactured by
Ikegai Co., Ltd.). Successively, each mixture was finely pulverized
by ultrasonic jet pulverizer Labo-Jet (manufactured by Nippon
Pneumatic Industry Co., Ltd.) and classified by an air current
classifier (MDS-I, manufactured by Nippon Pneumatic Industry Co.,
Ltd.) to obtain toner particles with 8 .mu.m of particle diameter
D50. Next, colloidal silica (Aerosil R972: manufactured by Nippon
Aerosil Co., Ltd.) 0.5 part was added to each obtained toner
particles 100 part and mixed by a sample mill to obtain toners (21)
to (23) within a scope of the invention and a toner (21) for
comparison.
The toners were evaluated by the above-mentioned evaluation methods
and the evaluation results are shown in Table 3. The image density
were measured by carrying out fixing evaluation in the same manner
as the above-mentioned MFT and measuring the density by a Macbeth
Densitometer.
TABLE-US-00004 TABLE 3 Grindability average particle MFT Gross HOT
diameter Image Toner No. (.degree. C.) (.degree. C.) (.degree. C.)
Fluidity (.mu.m) density Toner (21) 135 145 200 .largecircle. 11
1.31 Toner (22) 135 145 200 .largecircle. 11 1.30 Toner (23) 130
145 230 .largecircle. 11 1.35 Toner for 140 145 200 .DELTA.X 12
1.18 comparison (21)
Examples Relevant to the Fifth Invention
Production Examples 31 to 33 and Comparative Production Examples 31
and 32
Production Example 31
Polyester Resin
[Synthesis of Linear Polyester]
The linear polyester (Aa-1) of Example 1 was synthesized and
employed as linear polyester (Aa-31).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab-1) of Example 1 was synthesized and
employed as non-linear polyester (Ab-31).
Production Example 32
Polyester Resin
[Synthesis of Linear Polyester]
The linear polyester (Aa-2) of Example 2 was synthesized and
employed as linear polyester (Aa-32).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab-2) of Example 2 was synthesized and
employed as non-linear polyester (Ab-32).
Production Example 33
Additive for Toner
To an autoclave reaction tank equipped with a thermometer and a
stirrer, xylene 600 part, thermal degradation type low molecular
weight polypropylene (Viscol 440P: softening point 153.degree. C.,
manufactured by Sanyo Chemical Industries, Ltd.) 480 part, and
thermal degradation type low molecular weight polypropylene (Sanwax
LEL-400: softening point 128.degree. C., manufactured by Sanyo
Chemical Industries, Ltd.) 120 part were loaded and sufficiently
dissolved and after replacement of the gas with nitrogen, a mixed
solution containing styrene 1992 part, acrylonitrile 168 part,
monobutyl maleate 240 part, di-tert-butyl
peroxyhexahydroterephthalate 78 part, and xylene 455 part was
dropwise added at 175.degree. C. for 3 hours to carry out
polymerization and the temperature was kept further for 30 minutes.
Next, De-solvation was carried out to obtain an additive (B-1) for
a toner, which was modified wax.
The additive (B-1) had 2950 of Mn, 10900 of weight average
molecular weight, and 20.9 mgKOH/g of acid value.
Comparative Production Example 31
Polyester Resin
[Synthesis of Linear Polyester]
The linear polyester (Aa'-6) of Comparative Example 2 was
synthesized and employed as linear polyester (Aa'-31) for
comparison.
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab'-5) of Comparative Example 1 was
synthesized and employed as non-linear polyester (Ab'-31) for
comparison.
Comparative Production Example 32
To an autoclave reaction tank equipped with a thermometer and a
stirrer, xylene 1200 part was loaded and after replacement of the
gas with nitrogen, a mixed solution containing styrene 1992 part,
acrylonitrile 168 part, monobutyl maleate 240 part, di-tert-butyl
peroxyhexahydroterephthalate 78 part, and xylene 455 part was
dropwise added at 175.degree. C. for 3 hours to carry out
polymerization and the temperature was kept further for 30 minutes.
Next, De-solvation was carried out to obtain an additive (B'-1) for
a toner for comparison.
The additive (B'-1) had 2900 of Mn, 9800 of weight average
molecular weight, and 25.8 mgKOH/g of acid value.
Examples 31 and 32 and Comparative Examples 31 and 32
Example 31
[Production of Polyester Resin Composition for Toner]
The linear polyester (Aa-31) 580 part, the non-linear polyester
(Ab-31) 400 part, and the additive for a toner (B-1) 20 part were
melted and kneaded at 150.degree. C. jacket temperature for
stagnation duration 3 minutes by a continuous kneader. The
resulting melted resin was cooled to a room temperature and
successively pulverized by a pulverizer for granulation to obtain a
polyester resin composition (31) for a toner of the invention.
The polyester resin composition (31) for a toner had Tg of
64.degree. C., 2200 of Mn, 3200 of Mp, and 13% of the THF-insoluble
fractions.
Example 32
[Production of Polyester Resin Composition for Toner]
The linear polyester (Aa-32) 580 part, the non-linear polyester
(Ab-32) 400 part, and the additive for a toner (B-1) 20 part were
melted and kneaded at 150.degree. C. jacket temperature for
stagnation duration 3 minutes by a continuous kneader. The
resulting melted resin was cooled to a room temperature and
successively pulverized by a pulverizer for granulation to obtain a
polyester resin composition for a toner (32) of the invention.
The polyester resin composition for a toner (32) had Tg of
64.degree. C., 3200 of Mn, 6700 of Mp, and 13% of the THF-insoluble
fractions.
Comparative Example 31
[Production of Polyester Resin Composition for Toner]
The linear polyester (Aa'-31) 580 part, the non-linear polyester
(Ab'-31) 400 part, and the additive for a toner (B-1) 20 part were
melted and kneaded at 150.degree. C. jacket temperature for
stagnation duration 3 minutes by a continuous kneader. The
resulting melted resin was cooled to a room temperature and
successively pulverized by a pulverizer for granulation to obtain a
polyester resin composition (31) for a toner for comparison.
The polyester resin composition (31) for a toner for comparison had
Tg of 64.degree. C., 3200 of Mn, 6700 of Mp, and 13% of the
THF-insoluble fractions.
Comparative Example 32
[Production of Polyester Resin Composition for Toner]
The linear polyester (Aa-32) 580 part, the non-linear polyester
(Ab-32) 400 part, and the additive for a toner (B'-1) for
comparison 20 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin composition (32) for a
toner for comparison.
The polyester resin composition (32) for a toner for comparison had
Tg of 64.degree. C., 3200 of Mn, 6700 of Mp, and 13% of the
THF-insoluble fractions.
Evaluation Examples (31) and (32) and Comparative Evaluation
Examples (31) and (32)
Carbon black MA-100 (manufactured by Mitsubishi Chemical Corp.) 8
part, carnauba wax 5 part, a charge control agent T-77
(manufactured by Hodogaya Chemical Co., Ltd.) 1 part were added to
respective resin compositions for a toner (31) and (32) within the
scope of the invention and resin compositions for a toner for
comparison (31) and (32) and toners were produced by the following
method.
At first, each mixture was preliminarily mixed by a Henshel mixer
(FM10B, manufactured by Mitsui Miike Chemical Plant Service Inc.)
and then kneaded by a biaxial kneader (PCM-30, manufactured by
Ikegai Co., Ltd.). Successively, each mixture was finely pulverized
by ultrasonic jet pulverizer Labo-Jet (manufactured by Nippon
Pneumatic Industry Co., Ltd.) and classified by an air current
classifier (MDS-I, manufactured by Nippon Pneumatic Industry Co.,
Ltd.) to obtain toner particles with 8 .mu.m of particle diameter
D50. Next, colloidal silica (Aerosil R972: manufactured by Nippon
Aerosil Co., Ltd.) 0.5 part was added to each obtained toner
particles 100 part and mixed by a sample mill to obtain toners (31)
and (32) within a scope of the invention and toners (31) and (32)
for comparison.
The toners were evaluated by the following evaluation methods and
the evaluation results are shown in Table 4.
TABLE-US-00005 TABLE 4 MFT HOT Toner Image Toner No. (.degree. C.)
(.degree. C.) fluidity stability Toner (31) 120 230 .largecircle.
.largecircle. Toner (32) 120 230 .largecircle. .largecircle. Toner
for 135 230 .DELTA. .DELTA. comparison (31) Toner for 130 210 X X
comparison (32)
[Evaluation Methods] [1] Minimum fixing temperature (MFT)
According to the above-mentioned method. [2] Hot offset occurrence
temperature (HOT)
According to the above-mentioned method. [3] Toner fluidity
According to the above-mentioned method. [4] Image stability
Using a commercialized printer (LP-1300), each produced toner was
loaded and mat printing was carried out continuously. The image of
the 5000th printing was observed by eye observation and the image
stability was evaluated according to the following criteria. No
unevenness and no white streak: .largecircle. White streaks
slightly observed but no unevenness: .DELTA. White streaks observed
and unevenness noticeable: x
Examples Relevant to the Sixth Invention
Production Examples 41 to 43 and Comparative Production Examples 41
to 44
Production Example 41
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
792 part (22.8 mole), terephthalic acid dimethyl ester 868 part
(9.8 mole), adipic acid 13 part (0.2 mole), and as a condensation
catalyst, tetrabutoxy titanate 3 part were loaded and under
nitrogen gas stream, reaction was carried out at 180.degree. C. for
8 hours while the produced methanol was removed. Successively,
while the reaction system was gradually heated to 230.degree. C.
and the produced propylene glycol and water were removed under
nitrogen gas stream, reaction was carried out for 4 hours and
further continued at a pressure reduced to 5 to 20 mmHg and when
the softening point (Tm) reached 80.degree. C., the reaction system
was cooled to 180.degree. C. and trimellitic anhydride 26 part (0.3
mole) was added and after 2 hour reaction in closed state at a
normal pressure, the product was discharged. The recovered
propylene glycol was 410 part (11.8 mole). After being cooled to a
room temperature, the discharged resin was pulverized for
granulation. The obtained product was linear polyester (Aa-41).
The linear polyester (Aa-41) had Tg of 56.degree. C., 2200 of Mn,
4000 of Mp, 0% of the THF-insoluble fractions, 73 kJ of En,
2.times.10.sup.2 of G', Tm of 82.degree. C., 4 to 12 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 810
part (22.4 mole), terephthalic acid dimethyl ester 774 part (8.4
mole), adipic acid 111 part (1.6 mole), and as a condensation
catalyst, tetrabutoxy titanate 3 part were loaded and under
nitrogen gas stream, reaction was carried out at 180.degree. C. for
8 hours while the produced methane was removed. Successively, while
the reaction system was gradually heated to 230.degree. C. and the
produced propylene glycol and water were removed under nitrogen gas
stream, reaction was carried out for 4 hours and further continued
for 1 hour at a pressure reduced to 5 to 20 mmHg. The recovered
propylene glycol was 427 part (11.8 mole). Then the reaction system
was cooled to 180.degree. C., trimellitic anhydride 18 part (0.2
mole) was added and after 2-hour reaction in closed state at a
normal pressure, reaction was carried out at 220.degree. C. in a
pressure reduced to 5 to 20 mmHg and when the softening point (Tm)
reached 125.degree. C., the product was discharged and cooled to a
room temperature and pulverized for granulation. The obtained
product was non-linear polyester (Ab-41).
The non-linear polyester (Ab-41) had Tg of 55.degree. C., 7000 of
Mn, 16000 of Mp, 3% of the THF-insoluble fractions, 73 kJ of En,
6.8.times.10.sup.2 of G', Tm of 125.degree. C., and 2.8 to 4 of tan
.delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-41) 600 part and the non-linear polyester
(Ab-41) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A-41) for a toner of the
invention.
The polyester resin (A-41) for a toner had Tg of 55.degree. C., Sp
of 98.degree. C., 4500 of Mn, 5000 of Mp, and 2% of the
THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was within
the area surrounded with the equations (1) to (4).
Production Example 42
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
803 part (22.6 mole), terephthalic acid dimethyl ester 816 part
(9.0 mole), adipic acid 68 part (1.0 mole), and as a condensation
catalyst, tetrabutoxy titanate 3 part were loaded and under
nitrogen gas stream, reaction was carried out at 180.degree. C. for
8 hours while the produced methanol was removed. Successively,
while the reaction system was gradually heated to 230.degree. C.
and the produced propylene glycol and water were removed under
nitrogen gas stream, reaction was carried out for 4 hours and
further continued at a pressure reduced to 5 to 20 mmHg and when
the softening point (Tm) reached 93.degree. C., the reaction system
was cooled to 180.degree. C. and trimellitic anhydride 26 part (0.3
mole) was added and after 2 hour reaction in closed state at a
normal pressure, the product was discharged. The recovered
propylene glycol was 427 part (12.0 mole). After being cooled to a
room temperature, the discharged resin was pulverized for
granulation. The obtained product was linear polyester (Aa-42).
The linear polyester (Aa-42) had Tg of 55.degree. C., 3000 of Mn,
5800 of Mp, 0% of the THF-insoluble fractions, 73kJ of En,
2.2.times.10.sup.2 of G', Tm of 95.degree. C., 5 to 11 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 780
part (22.6 mole), terephthalic acid dimethyl ester 793 part (9.0
mole), adipic acid 66 part (1.0 mole), and as a condensation
catalyst, tetrabutoxy titanate 3 part were loaded and under
nitrogen gas stream, reaction was carried out at 180.degree. C. for
8 hours while the produced methanol was removed. Successively,
while the reaction system was gradually heated to 230.degree. C.
and the produced propylene glycol and water were removed under
nitrogen gas stream, reaction was carried out for 4 hours and
further continued for 1 hour at a pressure reduced to 5 to 20 mmHg.
The recovered propyleneglycol was 397 part (11.5 mole) Then the
reaction system was cooled to 180.degree. C., trimellitic anhydride
44 part (0.5 mole) was added and after 2-hour reaction in closed
state at a normal pressure, reaction was carried out at 220.degree.
C. in a pressure reduced to 5 to 20 mmHg and when the softening
point (Tm) reached 145.degree. C., the product was discharged and
cooled to a room temperature and pulverized for granulation. The
obtained product was non-linear polyester (Ab-42).
The non-linear polyester (Ab-42) had Tg of 66.degree. C., 6800 of
Mn, 10500 of Mp, 2% of the THF-insoluble fractions, 73 kJ of En,
2.0.times.10.sup.3 of G', Tm of 145.degree. C., and 1.5 to 1.9 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-42) 600 part and the non-linear polyester
(Ab-42) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A-42) for a toner of the
invention.
The polyester resin (A-42) for a toner had Tg of 60.degree. C.,
110.degree. C. of Sp, 5000 of Mn, 6500 of Mp, and 1% of the
THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was within
the area surrounded with the equations (1) to (4).
Production Example 43
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
634 part (22.7 mole), bisphenol A-2 mole PO adduct 256 part (2.0
mole), terephthalic acid dimethyl ester 658 part (9.2 mole), adipic
acid 43 part (0.8 mole), and as a condensation catalyst,
tetrabutoxy titanate 3 part were loaded and under nitrogen gas
stream, reaction was carried out at 180.degree. C. for 8 hours
while the produced methanol was removed. Successively, while the
reaction system was gradually heated to 230.degree. C. and the
produced propylene glycol and water were removed under nitrogen gas
stream, reaction was carried out for 4 hours and further continued
at a pressure reduced to 5 to 20 mmHg and when the softening point
(Tm) reached 93.degree. C., the reaction system was cooled to
180.degree. C. and trimellitic anhydride 26 part (0.4 mole) was
added and after 2 hour reaction in closed state at a normal
pressure, the product was discharged. The recovered propylene
glycol was 390 part (13.9 mole). After being cooled to a room
temperature, the discharged resin was pulverized for granulation.
The obtained product was linear polyester (Aa-43).
The linear polyester (Aa-43) had Tg of 65.degree. C., 3300 of Mn,
6200 of Mp, 0% of the THF-insoluble fractions, 90kJ of En,
2.2.times.10.sup.2 of G', Tm of 95.degree. C., 5 to 11 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 582
part (22.7 mole), bisphenol A-3 mole PO adduct 326 part (2.4 mole),
terephthalic acid dimethyl ester 603 part (9.2 mole), adipic acid
39 part (0.8 mole), and as a condensation catalyst, tetrabutoxy
titanate 3 part were loaded and under nitrogen gas stream, reaction
was carried out at 180.degree. C. for 8 hours while the produced
methanol was removed. Successively, while the reaction system was
gradually heated to 230.degree. C. and the produced propylene
glycol and water were removed under nitrogen gas stream, reaction
was carried out for 4 hours and further continued for 1 hour at a
pressure reduced to 5 to 20 mmHg. The recovered propylene glycol
was 360 part (14.0 mole). Then the reaction system was cooled to
180.degree. C., trimellitic anhydride 23 part (0.4 mole) was added
and after 2-hour reaction in closed state at a normal pressure,
reaction was carried out at 220.degree. C. in a pressure reduced to
5 to 20 mmHg and when the softening point (Tm) reached 160.degree.
C., the product was discharged and cooled to a room temperature and
pulverized for granulation. The obtained product was non-linear
polyester (Ab-43).
The non-linear polyester (Ab-43) had Tg of 65.degree. C., 7000 of
Mn, 13200 of Mp, 3% of the THF-insoluble fractions, 97 kJ of En,
9.5.times.10.sup.3 of G', 160.degree. C. of Tm, and 1.2 to 2.2 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa-43) 600 part and the non-linear polyester
(Ab-43) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A-43) for a toner of the
invention.
The polyester resin (A-43) for a toner had Tg of 65.degree. C., Sp
of 125.degree. C., 5100 of Mn, 6500 of Mp, and 2% of the
THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was within
the area surrounded with the equations (1) to (4).
Comparative Production Example 41
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
PO adduct 642 part (11.9 mole), bisphenol A-3 mole PO adduct 131
part (2.1 mole), terephthalic acid 275 part (10.0 mole), and as a
condensation catalyst tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 230.degree.
C. for 5 hours while the produced water was removed. Successively,
reaction was carried out under a pressure reduced to 5 to 20 mmHg
and when the acid value reached 2 or lower, the reaction system was
cooled to 180.degree. C. and trimellitic anhydride 26 part (0.9
mole) was added and the product was discharged after reaction for 2
hours in closed condition at a normal pressure and after cooled to
a room temperature, the discharged resin was pulverized for
granulation. The obtained product was linear polyester
(Aa'-41).
The linear polyester (Aa'-41) had Tg of 55.degree. C., 2000 of Mn,
4000 of Mp, 0% of the THF-insoluble fractions, 170 kJ of En,
2.0.times.10.sup.2 of G', Tm of 82.degree. C., 4 to 12 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, bisphenol A-3 mole PO
adduct 777 part (12.5 mole), terephthalic acid 171 part (6.7 mole),
trimellitic anhydride 59 part (2.0 mole), and as a condensation
catalyst, tetrabutoxy titanate 3 part were loaded and under
nitrogen gas stream, reaction was carried out at 230.degree. C. for
7 hours while the produced water was removed. Successively,
reaction was carried out under a pressure reduced to 5 to 20 mmHg
and when the acid value reached 2 or lower, the reaction system was
cooled to 180.degree. C. and fumaric acid 60 part (3.3 mole) was
added and after 4 our reaction at a normal pressure, the reaction
was carried out in a pressure reduced to 5 to 20 mmHg and when the
softening point (Tm) reached 115.degree. C., the product was
discharged, cooled to a room temperature, and then pulverized for
granulation. The obtained product was non-linear polyester
(Ab'-41).
The non-linear polyester (Ab'-41) had Tg of 56.degree. C., 6500 of
Mn, 9500 of Mp, 5% of the THF-insoluble fractions, 184 kJ of En,
6.8.times.10.sup.2 of G', Tm of 125.degree. C., and 0.7 to 1.1 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-41) 600 part and the non-linear polyester
(Ab'-41) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A'-41) for a toner for
comparison.
The polyester resin (A'-41) for a toner for comparison had Tg of
56.degree. C., Sp of 96.degree. C., 4000 of Mn, 5000 of Mp, 3% of
the THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was
within the area surrounded with the equations (1) to (4).
Comparative Production Example 42
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, bisphenol A-2 mole
PO adduct 490 part (8.4 mole), bisphenol A-3 mole PO adduct 266
part (4.0 mole), terephthalic acid 278 part (10.0 mole), and as a
condensation catalyst tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 230.degree.
C. for 5 hours while the produced water was removed. Successively,
reaction was carried out under a pressure reduced to 5 to 20 mmHg
and when the acid value reached 2 or lower, the reaction system was
cooled to 180.degree. C. and trimellitic anhydride 26 part (0.8
mole) was added and the product was discharged after reaction for 2
hours in closed condition at a normal pressure and after cooled to
a room temperature, the discharged resin was pulverized for
granulation. The obtained product was linear polyester
(Aa'-42).
The linear polyester (Aa'-42) had Tg of 65.degree. C., 3000 of Mn,
5900 of Mp, 0% of the THF-insoluble fractions, 172 kJ of En,
2.3.times.10.sup.2 of G', Tm of 95.degree. C., 5 to 11 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, bisphenol A-2 mole PO
adduct 210 part (4.2 mole), bisphenol A-3 mole PO adduct 567 part
(9.8 mole), terephthalic acid 159 part (6.7 mole), fumaric acid 56
part (3.3 mole), and as a condensation catalyst, tetrabutoxy
titanate 3 part were loaded and under nitrogen gas stream, reaction
was carried out at 210.degree. C. for 7 hours while the produced
water was removed. Successively, reaction was carried out under a
pressure reduced to 5 to 20 mmHg and when the acid value reached 2
or lower, the reaction system was cooled to 180.degree. C. and
trimellitic acid 74 part (2.7 mole) was added and after 2 our
reaction at a normal pressure, the reaction was carried out at
220.degree. C. in a pressure reduced to 5 to 20 mmHg and when the
softening point (Tm) reached 160.degree. C., the product was
discharged, cooled to a room temperature, and then pulverized for
granulation. The obtained product was non-linear polyester
(Ab'-42).
The non-linear polyester (Ab'-42) had Tg of 67.degree. C., 4000 of
Mn, 7500 of Mp, 45% of the THF-insoluble fractions, 179 kJ of En,
1.2.times.10.sup.4 of G', Tm of 160.degree. C., and 0.5 to 0.8 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-42) 600 part and the non-linear polyester
(Ab'-42) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A'-42) for a toner for
comparison.
The polyester resin (A'-42) for a toner for comparison had Tg of
66.degree. C., Sp of 125.degree. C., 3500 of Mn, 6000 of Mp, 23% of
the THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was
within the area surrounded with the equations (1) to (4).
Comparative Production Example 43
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
385 part (22.6 mole), bisphenol A-2 mole PO adduct 156 part (2.0
mole), bisphenol A-3 mole PO adduct 451 part (5.0 mole),
terephthalic acid dimethyl ester 391 part (9.0 mole), adipic acid
33 part (1.0 mole), and as a condensation catalyst, tetrabutoxy
titanate 3 part were loaded and under nitrogen gas stream, reaction
was carried out at 180.degree. C. for 8 hours while the produced
methanol was removed. Successively, while the reaction system was
gradually heated to 230.degree. C. and the produced propylene
glycol and water were removed under nitrogen gas stream, reaction
was carried out for 4 hours and further continued at a pressure
reduced to 5 to 20 mmHg and when the softening point (Tm) reached
93.degree. C., the reaction system was cooled to 180.degree. C. and
trimellitic anhydride 26 part (0.6 mole) was added and after 2 hour
reaction in closed state at a normal pressure, the product was
discharged. The recovered propylene glycol was 304 part (17.9
mole). After being cooled to a room temperature, the discharged
resin was pulverized for granulation. The obtained product was
linear polyester (Aa'-43).
The linear polyester (Aa'-43) had Tg of 52.degree. C., 2900 of Mn,
5800 of Mp, 0% of the THF-insoluble fractions, 136 kJ of En,
2.3.times.10.sup.2 of G', Tm of 95.degree. C., 5 to 11 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 132
part (8.0 mole), bisphenol A-3 mole PO adduct 653 part (7.5 mole),
terephthalic acid dimethyl ester 140 part (3.3 mole), trimellitic
anhydride 83 part (2.0 mole), and as a condensation catalyst,
tetrabutoxy titanate 3 part were loaded and under nitrogen gas
stream, reaction was carried out at 180.degree. C. for 8 hours
while the produced methanol was removed. Successively, while the
reaction system was gradually heated to 230.degree. C. and the
produced propylene glycol and water were removed under nitrogen gas
stream, reaction was carried out for 4 hours and further continued
for 1 hour at a pressure reduced to 5 to 20 mmHg. The recovered
propylene glycol was 61 part (3.7 mole). Then the reaction system
was cooled to 180.degree. C., fumaric acid 167 part (6.7 mole) was
added and after 4-hour reaction at a normal pressure, reaction was
carried out under a pressure reduced to 5 to 20 mmHg and when the
softening point (Tm) reached 130.degree. C., the product was
discharged and cooled to a room temperature and pulverized for
granulation. The obtained product was non-linear polyester
(Ab'-43).
The non-linear polyester (Ab'-43) had Tg of 52.degree. C., 6500 of
Mn, 10000 of Mp, 5% of the THF-insoluble fractions, 143 kJ of En,
1.8.times.10.sup.3 of G', Tm of 130.degree. C., and 0.7 to 1.1 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-43) 600 part and the non-linear polyester
(Ab'-43) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A'-43) for a toner of the
invention.
The polyester resin (A'-43) for a toner had Tg of 52.degree. C., Sp
of 108.degree. C., 4500 of Mn, 6500 of Mp, and 3% of the
THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was out of
the area surrounded with the equations (1) to (4).
Comparative Production Example 44
[Synthesis of Linear Polyester]
To the reaction tank same as that of Example 1, propylene glycol
329 part (22.9 mole), bisphenol A-2 mole PO adduct 395 part (6.0
mole), bisphenol A-3 mole PO adduct 304 part (4.0 mole),
terephthalic acid dimethyl ester 363 part (9.9 mole), adipic acid 3
part (0.1 mole), and as a condensation catalyst, tetrabutoxy
titanate 3 part were loaded and under nitrogen gas stream, reaction
was carried out at 180.degree. C. for 8 hours while the produced
methanol was removed. Successively, while the reaction system was
gradually heated to 230.degree. C. and the produced propylene
glycol and water were removed under nitrogen gas stream, reaction
was carried out for 4 hours and further continued at a pressure
reduced to 5 to 20 mmHg and when the softening point (Tm) reached
95.degree. C., the reaction system was cooled to 180.degree. C. and
trimellitic anhydride 26 part (0.7 mole) was added and after 2 hour
reaction in closed state at a normal pressure, the product was
discharged. The recovered propylene glycol was 299 part (20.8
mole). After being cooled to a room temperature, the discharged
resin was pulverized for granulation. The obtained product was
linear polyester (Aa'-44).
The linear polyester (Aa'-44) had Tg of 77.degree. C., 3000 of Mn,
6000 of Mp, 0% of the THF-insoluble fractions, 156 kJ of En,
2.4.times.10.sup.2 of G', Tm of 97.degree. C., 2 to 8 of tan
.delta..
[Synthesis of Non-linear Polyester]
To the reaction tank same as described above, propylene glycol 330
part (22.6 mole), bisphenol A-2 mole PO adduct 656 part (9.8 mole),
terephthalic acid dimethyl ester 373 part (10.0 mole), and as a
condensation catalyst, tetrabutoxy titanate 3 part were loaded and
under nitrogen gas stream, reaction was carried out at 180.degree.
C. for 8 hours while the produced methanol was removed.
Successively, while the reaction system was gradually heated to
230.degree. C. and the produced propylene glycol and water were
removed under nitrogen gas stream, reaction was carried out for 4
hours and further continued for 1 hour at a pressure reduced to 5
to 20 mmHg. The recovered propylene glycol was 297 part (20.3
mole). Then the reaction system was cooled to 180.degree. C.,
trimellitic anhydride 74 part (2.0 mole) was added and after 2-hour
reaction in closed state at a normal pressure, reaction was carried
out at 230.degree. C. under a pressure reduced to 5 to 20 mmHg and
when the softening point (Tm) reached 132.degree. C., the product
was discharged and cooled to a room temperature and pulverized for
granulation. The obtained product was non-linear polyester
(Ab'-44).
The non-linear polyester (Ab'-44) had Tg of 77.degree. C., 6600 of
Mn, 9800 of Mp, 5% of the THF-insoluble fractions, 149 kJ of En,
1.9.times.10.sup.3 of G', Tm of 132.degree. C., and 0.7 to 1.1 of
tan .delta..
[Production of Polyester Resin for Toner]
The linear polyester (Aa'-44) 600 part and the non-linear polyester
(Ab'-44) 400 part were melted and kneaded at 150.degree. C. jacket
temperature for stagnation duration 3 minutes by a continuous
kneader. The resulting melted resin was cooled to a room
temperature and successively pulverized by a pulverizer for
granulation to obtain a polyester resin (A'-44) for a toner of the
invention.
The polyester resin (A'-43) for a toner had Tg of 77.degree. C., Sp
of 110.degree. C., 4200 of Mn, 6600 of Mp, and 3% of the
THF-insoluble fractions. As shown in FIG. 1, Tg and Sp was out of
the area surrounded with the equations (1) to (4).
Examples 41 to 43 and Comparative Example 41 to 44
A yellow pigment (Toner Yellow HG VP2155, manufactured by Clariant
Japan K.K.) 4 part, carnauba wax 5 part, a charge control agent
T-77 (manufactured by Hodogaya Chemical Co., Ltd.) 1 part were
added to respective polyester resins for a toner (A-41) to (A-43)
within the scope of the invention and polyester resins for a toner
(A'-41) to (A'-44) for comparison and toners were produced by the
following method.
At first, each mixture was preliminarily mixed by a Henshel mixer
(FM10B, manufactured by Mitsui Miike Chemical Plant Service Inc.)
and then kneaded by a biaxial kneader (PCM-30, manufactured by
Ikegai Co., Ltd.). Successively, each mixture was finely pulverized
by ultrasonic jet pulverizer Labo-Jet (manufactured by Nippon
Pneumatic Industry Co., Ltd.) and classified by an air current
classifier (MDS-I, manufactured by Nippon Pneumatic Industry Co.,
Ltd.)to obtain toner particles with 8 im of particle diameter D50.
Next, colloidal silica (Aerosil R972: manufactured by Nippon
Aerosil Co., Ltd.) 0.5 part was added to each obtained toner
particles 100 part and mixed by a sample mill to obtain toners (41)
to (43) within a scope of the invention and toners (41) to (44) for
comparison.
The toners were evaluated by the following evaluation methods and
the evaluation results are shown in Table 5.
TABLE-US-00006 TABLE 5 MFT HOT Color Grindability average Toner No.
(.degree. C.) (.degree. C.) tone particle diameter (.mu.m) Toner
(41) 120 225 .largecircle. 11 Toner (42) 120 230 .largecircle. 11
Toner (43) 120 230 .largecircle. 11 Toner for 120 225 .DELTA. 13
comparison (41) Toner for 125 230 X 15 comparison (42) Toner for
120 215 .DELTA. 12 comparison (43) Toner for 130 225 X 14
comparison (44)
[Evaluation Methods] [1] Minimum fixing temperature (MFT)
According to the above-mentioned method. [2] Hot offset occurrence
temperature (HOT)
According to the above-mentioned method. [3] Color tone
In the same manner as the above-mentioned MFT, an image was fixed
on an OHP film at a fixing roll temperature of 170.degree. C. and
the fixed image was projected by an overhead projector and the
color tone was evaluated by eye observation. Judgment Criteria:
.largecircle.: clear pale yellow color, .DELTA.: clear yellow
color, and x: slightly foggy yellow color [4] Grindability
According to the above-mentioned method.
Examples Relevant to the Seventh and the Eighth Inventions
Production Examples 51 to 53
Production Example 51
Production of Water-based Medium
To a reaction container equipped with a stirring rod and a
thermometer, water 753 part, alkylallylsulfosuccinic acid sodium
salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries,
Ltd.) 8 part, styrene 58 part, methacrylic acid 58 part, butyl
acrylate 77 part, ammonium persulfate 1 part, and a surfactant
(polyoxysorbitan monooleate) 9 part were loaded and the mixture was
stirred at 400 rpm for 15 minutes to obtain a white emulsion. The
emulsion was heated to 75.degree. C. temperature of the system and
reacted for 5 hours. Further an aqueous 1% ammonium persulfate
solution 30 part was added, the reaction product was aged at
75.degree. C. for 5 hours to obtain a water-based dispersion of
vinyl resin (styrene-methacrylic acid-butyl acrylate-sodium
alkylallylsulfosuccinate copolymer).
Further, carboxymethyl cellulose sodium salt 2 part, an aqueous
solution of 48.5% of dodecyl diphenyl ether disulfonic acid sodium
salt (Eleminol MON-7, manufactured by Sanyo Chemical Industries,
Ltd.) 40 part, and ion exchange water 443 part were added to the
above-mentioned water-based dispersion 15 part and evenly stirred
to obtain a water-based medium. The volume average particle
diameter of the obtained water-based medium measured by LA-920 was
0.05 .mu.m.
Production Example 52
Production of Colorant Dispersion
Copper phthalocyanine 20 part, a colorant dispersion (Solsperse
28000: manufactured by Avecia K.K.) 4 part, and ethyl acetate 76
part were loaded to a beaker and stirred and evenly dispersed and
then the copper phthalocyanine was micro-dispersed by a bead mill
to obtain [Colorant dispersion]. The volume average particle
diameter of the obtained [Colorant dispersion] measured by LA-920
was 0.3 pm.
Production Example 53
Production of Release Agent Dispersion
Paraffin wax 20 part and ethyl acetate 80 part were loaded to a
beaker and stirred and evenly dispersed and then the paraffin wax
was micro-dispersed by a bead mill to obtain [Release agent
dispersion]. The volume average particle diameter of the obtained
[Release agent dispersion] measured by LA-920 was 0.5 .mu.m.
Examples 51 to 55 and Comparative Examples 51 to 54
Example 51
[Synthesis of Linear Polyester]
The linear polyester (Aa-1) of Example 1 was synthesized and
employed as linear polyester (K1a-51).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab-1) of Example 1 was synthesized and
employed as non-linear polyester (K1b-51).
[Production of Oil Type Mixed Solution]
The linear polyester (K1a-51) 24 part, the non-linear polyester
(K1b-51) 16 part, [Colorant dispersion] produced in Production
Example 5210 part, [Release agent dispersion] produced in
Production Example 5325 part, and ethyl acetate 25 part were mixed
and stirred evenly to obtain an oil type mixed solution (I-1).
[Production of Resin Particles]
The oil type mixed solution (I-1) 40 part was added to the
[Water-based medium] produced in Production Example 5160 part and
stirred at 12000 rpm for 3 minutes by TK type homomixer. Next, the
mixed solution was transferred to a flask equipped with a stirring
blade and a thermometer and heated by a hot bath at 40.degree. C.
under reduced pressure to remove ethyl acetate and obtain a
water-based dispersion of resin particles. Next, the dispersion was
filtered and separated particles were dried at 40.degree. C. for 18
hours by an air circulation drying apparatus to obtain resin
particles (51).
Example 52
[Synthesis of Linear Polyester]
The linear polyester (Aa-2) of Example 2 was synthesized and
employed as linear polyester (K1a-52).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab-2) of Example 2 was synthesized and
employed as non-linear polyester (K1b-52).
[Production of Oil Type Mixed Solution]
An oil type mixed solution (I-2) was obtained in the same manner as
Example 51, except that the linear polyester (K1a-52) was used in
place of the linear polyester (K1a-51) and the non-linear polyester
(K1b-52) was used in place of the non-linear polyester
(K1b-51).
[Production of Resin Particles]
Resin particles (52) were obtained in the same manner as Example
51, except that the oil type mixed solution (I-2) was used in place
of the oil type mixed solution (I-1).
Example 53
[Synthesis of Linear Polyester]
The linear polyester (Aa-3) of Example 3 was synthesized and
employed as linear polyester (K1a-53).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab-3) of Example 3 was synthesized and
employed as non-linear polyester (K1b-53).
[Production of Oil Type Mixed Solution]
An oil type mixed solution (I-3) was obtained in the same manner as
Example 51, except that the linear polyester (K1a-53) was used in
place of the linear polyester (K1a-51) and the non-linear polyester
(K1b-53) was used in place of the non-linear polyester
(K1b-51).
[Production of Resin Particles]
Resin particles (53) were obtained in the same manner as Example
51, except that the oil type mixed solution (I-3) was used in place
of the oil type mixed solution (I-1).
Example 54
[Synthesis of Linear Polyester]
The linear polyester (Aa-4) of Example 4 was synthesized and
employed as linear polyester (K1a-54).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab-4) of Example 4 was synthesized and
employed as non-linear polyester (K1b-54).
[Production of Oil Type Mixed Solution]
An oil type mixed solution (I-4) was obtained in the same manner as
Example 51, except that the linear polyester (K1a-54) was used in
place of the linear polyester (K1a-51) and the non-linear polyester
(K1b-54) was used in place of the non-linear polyester
(K1b-51).
[Production of Resin Particles]
Resin particles (54) were obtained in the same manner as Example
51, except that the oil type mixed solution (I-4) was used in place
of the oil type mixed solution (I-1).
Example 55
[Synthesis of Styrene-Acryl Resin]
After replacement of the gas with nitrogen, xylene 150 part was
loaded to a 1 L autoclave and heated to 150.degree. C. in closed
state under stirring condition. A mixed solution containing styrene
425 part, n-butyl acrylate 75 part, dibutyl peroxide 5 part, and
xylene 95 part was dropwise added for 3 hours while the temperature
in the autoclave was kept at 150.degree. C. to carry out
polymerization. After that, the temperature was kept as it was for
1 hour to complete the polymerization. The obtained polymer
solution was vacuum dried at 180.degree. C. and cooled to a room
temperature and pulverized to obtain a polymer (G1). The obtained
styrene-acrylic resin (G1) had 7500 of Mn and 1400 of Mp.
[Production of Oil Type Mixed Solution]
The linear polyester (K1a-51) 20 part, the non-linear polyester
(K1b-51) 17 part, [Colorant dispersion] produced in Production
Example 52 10 part, [Release agent dispersion] produced in
Production Example 53 25 part, and ethyl acetate 25 part were mixed
and stirred evenly to obtain an oil type mixed solution (I-5).
[Production of Resin Particles]
The oil type mixed solution (I-5) 40 part was added to the
[Water-based medium] produced in Production Example 5160 part and
stirred at 12000 rpm for 3 minutes by TK type homomixer. Next, the
mixed solution was transferred to a flask equipped with a stirring
blade and a thermometer and heated by a hot bath at 40.degree. C.
under reduced pressure to remove ethyl acetate and obtain a
water-based dispersion of resin particles. Next, the dispersion was
filtered and separated particles were dried at 40.degree. C. for 18
hours by an air circulation drying apparatus to obtain resin
particles (55).
Comparative Example 51
[Synthesis of Linear Polyester]
The linear polyester (Aa'-5) of Comparative Example 1 was
synthesized and employed as linear polyester (K1a'-55).
[Synthesis of N0n-linear Polyester]
The non-linear polyester (Ab'-5) of Comparative Example 1 was
synthesized and employed as non-linear polyester (K1b'-55)
[Production of Oil Type Mixed Solution]
An oil type mixed solution (I-6) was obtained in the same manner as
Example 51, except that the linear polyester (K1a'-55) was used in
place of the linear polyester (K1a-51) and the non-linear polyester
(K1b'-55) was used in place of the non-linear polyester
(K1b-51).
[Production of Resin Particles]
Comparative resin particles (51) were obtained in the same manner
as Example 51, except that the oil type mixed solution (I-6) was
used in place of the oil type mixed solution (I-1).
Comparative Example 52
[Synthesis of Linear Polyester]
The linear polyester (Ab'-6) of Comparative Example 2 was
synthesized and employed as linear polyester (K1b'-56).
[Production of Oil Type Mixed Solution]
An oil type mixed solution (I-7) was obtained in the same manner as
Example 51, except that the linear polyester (K1a'-56) was used in
place of the linear polyester (K1a-51) and the non-linear polyester
(K1b'-55) was used in place of the non-linear polyester
(K1b-51).
[Production of Resin Particles]
Comparative resin particles (52) were obtained in the same manner
as Example 51, except that the oil type mixed solution (I-7) was
used in place of the oil type mixed solution (I-1).
Comparative Example 53
[Synthesis of Linear Polyester]
The linear polyester (Aa'-7) of Comparative Example 3 was
synthesized and employed as linear polyester (K1a'-57). Since the
polyester (K1a'-57) could not be turned to be resin, it was not
used for producing resin particles.
Comparative Example 54
[Synthesis of Linear Polyester]
The linear polyester (Aa'-8) of Comparative Example 4 was
synthesized and employed as linear polyester (K1a'-58).
[Synthesis of Non-linear Polyester]
The non-linear polyester (Ab'-8) of Comparative Example 4 was
synthesized and employed as non-linear polyester (K1b'-58)
[Production of Oil Type Mixed Solution]
An oil type mixed solution (I-8) was obtained in the same manner as
Example 51, except that the linear polyester (K1a'-58) was used in
place of the linear polyester (K1a-51) and the non-linear polyester
(K1b'-58) was used in place of the non-linear polyester
(K1b-51).
[Production of Resin Particles]
Comparative resin particles (54) were obtained in the same manner
as Example 51, except that the oil type mixed solution (I-8) was
used in place of the oil type mixed solution (I-1).
Evaluations were carried out by the following evaluation methods
and the evaluation results are shown in Table 6.
TABLE-US-00007 TABLE 6 Volume average MFT HOT Toner particle Resin
particle No. (.degree. C.) (.degree. C.) fluidity diameter (.mu.m)
Resin particle (51) 125 230 .largecircle..DELTA. 5.8 Resin particle
(52) 120 230 .largecircle. 5.7 Resin particle (53) 125 230
.largecircle. 5.8 Resin particle (54) 125 230 .largecircle. 6.0
Resin particle (55) 125 230 .largecircle. 5.8 Comparative resin 135
215 .DELTA.X 5.9 particles (51) Comparative resin 130 230 .DELTA.X
5.8 particles (52) Comparative resin 130 230 .DELTA. 5.6 particles
(54)
[Evaluation Methods] [1] Minimum fixing temperature (MFT)
According to the above-mentioned method. [2] Hot offset occurrence
temperature (HOT)
According to the above-mentioned method. [3] Toner fluidity
According to the above-mentioned method. [4] Volume average
particle diameter
The volume average primary particle diameter of resin particles was
measured by using Coulter Counter AT II (manufactured by US Coulter
Electronics Corp.).
Production Examples 61 to 68
Production Example 61
(Production of Water-based Dispersion Containing Resin Fine
Particles (Q-1))
To a reaction container equipped with a stirring rod and a
thermometer, styrene-modified phenol polyethylene oxide adduct
(Eleminol HB-12, manufactured by Sanyo Chemical Industries, Ltd.)
48 part and bisphenol A diglycidyl ether (Epikote 828, manufactured
by Yuka Shell Epoxy K. K.) 232 part were loaded and evenly
dissolved. Water was dropwise added to the reaction container under
stirring condition. When water 31 part was added, the reaction
system was emulsified and turned to be opaque. Further, water 224
part was dropwise added to obtain an emulsion. After the system was
heated to 70.degree. C. system temperature, a solution obtained by
dissolving ethylene diamine 20 part in water 446 part was dropwise
added for 2 hours while the temperature was kept at 70.degree. C.
as it was. On completion of the titration, the reaction system was
reacted and aged at 70.degree. C. for 5 hours and 90.degree. C. for
5 hours to obtain a water-based dispersion of amine-cured epoxy
resin (Q-1).
Further, carboxymethyl cellulose sodium salt 2 part, an aqueous
solution of 48.5% dodecyl diphenyl ether disulfonic acid sodium
salt (Eleminol MON-7, manufactured by Sanyo Chemical Industries,
Ltd.) 40 part and ion exchanged water 443 part were added to the
above-mentioned water-based dispersion 18 part and evenly stirred
to obtain a water-based dispersion containing the resin fine
particles (Q-1).
The volume average particle diameter of the resin fine particles
(Q-1) measured by laser type particle diameter distribution
measurement apparatus LA-920 (manufactured by Horiba Seisakusho)
was 0.81 .mu.m. Also, a portion of the water-based dispersion
containing the resin fine particles (Q-1) was centrifuged and
further subjected to the centrifugation by adding water two times
and dried to separate the resin component. Tg (measured by DSC,
hereinafter the same for Tg) of the resin component was 120.degree.
C.
Production Example 62
(Production of Water-based Dispersion Containing Resin Fine
Particles (Q-2))
To a reaction container equipped with a stirring rod and a
thermometer, styrene-modified phenol polyethylene oxide adduct
(Eleminol HB-12, manufactured by Sanyo Chemical Industries, Ltd.)
38 part, bisphenol A diglycidyl ether (Epikote 828, manufactured by
Yuka Shell Epoxy K. K.) 232 part, and dioctyl phthalate 10 part
were loaded and evenly dissolved. Water was dropwise added to the
reaction container under stirring condition. When water 31 part was
added, the reaction system was emulsified and turned to be opaque.
Further, water 224 part was dropwise added to obtain an emulsion
(1). After the system was heated to 70.degree. C. system
temperature, a solution obtained by dissolving ethylene diamine 20
part in water 446 part was dropwise added for 2 hours while the
temperature was kept at 70.degree. C. as it was. On completion of
the titration, the reaction system was reacted and aged at
70.degree. C. for 5 hours and 90.degree. C. for 5 hours to obtain a
water-based dispersion of amine-cured epoxy resin (Q-2).
Further, carboxymethyl cellulose sodium salt 2 part, an aqueous
solution of 48.5% dodecyl diphenyl ether disulfonic acid sodium
salt (Eleminol MON-7, manufactured by Sanyo Chemical Industries,
Ltd.) 40 part and ion exchanged water 443 part were added to the
above-mentioned water-based dispersion 18 part and evenly stirred
to obtain a water-based dispersion containing the resin fine
particles (Q-2).
The volume average particle diameter of the resin fine particles
(Q-1) measured by laser type particle diameter distribution
measurement apparatus LA-920 (manufactured by Horiba Seisakusho)
was 0.75 .mu.m. Also, a portion of the water-based dispersion
containing the resin fine particles (Q-2) was centrifuged and
further subjected to the centrifugation by adding water two times
and dried to separate the resin component. Tg (measured by DSC,
hereinafter the same for Tg) of the resin component was 114.degree.
C.
Production Example 63
(Production of Water-based Dispersion Containing Resin Fine
Particles (Q-3))
To a reaction container equipped with a stirring rod and a
thermometer, water 753 part, alkylallylsulfosuccinic acid sodium
salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries,
Ltd.) 8 part, styrene 58 part, methacrylic acid 58 part, butyl
acrylate 77 part, ammonium persulfate 1 part, and a surfactant
(polyoxysorbitan monooleate) 9 part were loaded and stirred at 400
rpm for 15 minutes to obtain an opaque emulsion. After the reaction
system was heated to 75.degree. C. system temperature, reaction was
carried out for 5 hours. Further, an aqueous 1% ammonium persulfate
solution 30 part was added and the reaction system aged at
75.degree. C. for 5 hours to obtain a water-based dispersion of
vinyl resin (styrene-methacrylic acid-butyl acrylate-sodium
alkylallylsulfosuccinate copolymer) (Q-3).
Further, carboxymethyl cellulose sodium salt 2 part, an aqueous
solution of 48.5% of dodecyl diphenyl ether disulfonic acid sodium
salt (Eleminol MON-7, manufactured by Sanyo Chemical Industries,
Ltd.) 40 part, and ion exchange water 443 part were added to the
above-mentioned water-based dispersion 15 part and evenly stirred
to obtain a water-based medium containing the vinyl resin
(Q-3).
The volume average particle diameter of the water-based dispersion
measured by electrophoresis particle diameter distribution
measurement apparatus ELS-8000 (manufactured by Otsuka Denshi) was
0.05 .mu.m. Also, a portion of the water-based dispersion
containing the resin fine particles (Q-3) was centrifuged and
further subjected to the centrifugation by adding water two times
and dried to separate the resin component. Tg was 75.degree. C.
Production Example 64
(Production of Water-based Dispersion Containing Resin Fine
Particles (Q-4))
To a reaction container equipped with a stirring rod and a
thermometer, water 753 part, alkylallylsulfosuccinic acid sodium
salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries,
Ltd.) 8 part, styrene 58 part, methacrylic acid 58 part, butyl
acrylate 72 part, E-84 (salicylic acid type metal complex:
manufactured by Olient Chemical Industries Ltd.) 5 part, ammonium
persulfate 1 part, and a surfactant (polyoxysorbitan monooleate) 9
part were loaded and stirred at 400 rpm for 15 minutes to obtain an
opaque emulsion. After the reaction system was heated to 75.degree.
C. system temperature, reaction was carried out for 5 hours.
Further, an aqueous 1% ammonium persulfate solution 30 part was
added and the reaction system aged at 75.degree. C. for 5 hours to
obtain a water-based dispersion of vinyl resin (styrene-methacrylic
acid-butyl acrylate-sodium alkylallylsulfosuccinate copolymer
containing the salicylic acid metal complex) (Q-4).
Further, carboxymethyl cellulose sodium salt 2 part, an aqueous
solution of 48.5% of dodecyl diphenyl ether disulfonic acid sodium
salt (Eleminol MON-7, manufactured by Sanyo Chemical Industries,
Ltd.) 40 part, and ion exchange water 443 part were added to the
above-mentioned water-based dispersion 15 part and evenly stirred
to obtain a water-based medium containing the vinyl resin (Q-4).
The volume average particle diameter of the water-based dispersion
measured by electrophoresis particle diameter distribution
measurement apparatus ELS-8000 was 0.05 .mu.m. Also, a portion of
the water-based dispersion containing the resin fine particles
(Q-4) was centrifuged and further subjected to the centrifugation
by adding water two times and dried to separate the resin
component. Tg was 80.degree. C.
Production Example 65
(Production of Curing Agent (.beta.-1))
To a reaction container equipped with a stirring rod and a
thermometer, ethylenediamine 50 part and MIBK 50 part were loaded
and reacted at 50.degree. C. for 5 hours. The obtained ketimine
compound is used as a curing agent (.beta.-1).
Production Example 66
(Production of Curing Agent (.beta.-2))
To a reaction container equipped with a stirring rod and a
thermometer, isophorone diisocyanate 45 part and MEK 55 part were
loaded and reacted at 50.degree. C. for 5 hours. The obtained
ketimine compound is used as a curing agent (.beta.-2).
Production Example 66
(Production of Colorant Dispersion Solution)
Copper phthalocyanine 20 part by weight and colorant dispersion
(Solsperse 28000: manufactured by Avecia K.K.) 4 part, and ethyl
acetate 76 part were loaded to a beaker and stirred and evenly
dispersed and then the copper phthalocyanine was micro-dispersed by
a bead mill to obtain [Colorant dispersion]. The volume average
particle diameter of the obtained [Colorant dispersion] measured by
LA-920 was 0.3 .mu.m.
Production Example 68
(Production of Release Agent Dispersion)
Paraffin wax 20 part and ethyl acetate 80 part were loaded to a
beaker and stirred and evenly dispersed and then the paraffin wax
was micro-dispersed by a bead mill to obtain [Release agent
dispersion]. The volume average particle diameter of the obtained
[Release agent dispersion] measured by LA-920 was 0.5 .mu.m.
Examples 61 to 66 and Comparative Example 61 to 64
Example 61
[Synthesis of Polyester (61)]
The linear polyester (Aa-1) of Example 1 was synthesized and
employed as polyester (61). Hydroxy value was 75 and acid value was
1.
[Synthesis of Polyurethane Resin (61)]
To the reaction tank same as that of Example 1, polyester (61) 68
part, isophorone diisocyanate 10 part, and ethyl acetate 78 part
were loaded and reaction was carried out at 75.degree. C. for 18
hours under nitrogen gas stream to obtain an ethyl acetate solution
of polyurethane resin (61). The polyurethane resin (61) had 3300 of
Mn, solid matter 50% in the polyurethane resin-containing ethyl
acetate solution, and 2,400 mPa.s of viscosity.
[Synthesis of Polyester (62)]
The linear polyester (Aa-2) of Example 2 was synthesized and
employed as polyester (62). Hydroxy value was 42 and acid value was
1.
[Production of Solvent Solution (p-1) of Resin (p)]
The polyester (62) 14 part, the ethyl acetate solution of
polyurethane resin. (61) 52 part, the [Colorant dispersion]
obtained by Production Example 62 10 part, the [Release agent
dispersion] obtained by Production Example 63 25 part, and ethyl
acetate 25 part were mixed and evenly stirred to obtain solvent
solution (p-1) of resin (p).
[Production of Resin Particles]
The solvent solution (p-1) of resin (p) 40 part was added to the
water-based dispersion containing resin fine particles (Q-1)
produced in Production Example 6160 part and stirred at 12000 rpm
for 3 minutes by TK type homomixer. Then, the mixed solution was
transferred to a flask equipped with a stirring blade and a
thermometer and heated by a hot bath at 40.degree. C. under reduced
pressure to remove ethyl acetate and obtain a water-based
dispersion of resin particles. Next, the dispersion was filtered
and separated particles were dried at 40.degree. C. for 18 hours by
an air circulation drying apparatus to obtain resin particles (61).
The resin particles (61) had Tg of 65.degree. C., 95 .mu.m of
particle diameter, and 0.0085 of volume average particle diameter
ratio to the resin fine particles (Q-1).
Further, MEK oxime-blocked HDI 20 part was added to the resin
particles (61) 100 part and the mixture was mixed by Henshel mixer
for 30 minutes to obtain a coating composition (1).
Example 62
[Synthesis of Isocyanate-containing Prepolymer (.alpha.-1)]
To the reaction tank same as that of Example 1, polyester (p-1) 31
part, isophorone diisocyanate 19 part, and ethyl acetate 50 part
were loaded and reaction was carried out at 75.degree. C. for 18
hours under nitrogen gas stream to obtain an ethyl acetate solution
of isocyanate-containing prepolymer (.alpha.-1). The
isocyanate-containing prepolymer (.alpha.-1) contains 50% of solid
matter and 2.1% content of isocyanate.
[Production of Solvent Solution (p-2) of Resin (p)]
The solvent solution (p-2) of resin (p) was obtained in the same
manner as Example 61, except that the ethyl acetate solution of
isocyanate-containing prepolymer (.alpha.-1) 52 part was used in
place of the ethyl acetate solution of polyurethane resin (1) 52
part and the curing agent (.beta.-1) produced in Production Example
655.3 part was used.
[Production of Resin Particles]
Resin particles (62) and a coating composition (62) were obtained
in the same manner as Example 61, except that the water-based
dispersion containing the resin fine particles (Q-2) was used in
place of the water-based dispersion containing the resin fine
particles (Q-1) and solvent solution (p-2) was used in place of the
solvent solution (p-1) of resin (p). The resin particles (62) had
Tg of 70.degree. C., 120 .mu.m of particle diameter, and 0.0063 of
volume average particle diameter ratio to the resin fine particles
(Q-2).
Example 63
[Synthesis of Styrene-acrylic Copolymer]
Ethyl acetate 160 part was loaded to a reaction container equipped
with a cooling tube, a stirrer, and a nitrogen introduction tube
and heated to 75.degree. C. and successively, a mixed solution
containing styrene 40 part, butylmethacrylate 120 part, acrylic
acid 60 part, ethyl acetate 60 part, and azobis(isobutyronitrile)
0.3 part was dropwise added for 4 hours and further azobis
(isobutyronitrile) 0.5 part was additionally added and the reaction
system was aged at 75.degree. C. for 8 hours to obtain a resin
solution containing styrene-acryl copolymer with 4,200 of Mn, 0 of
hydroxy value, 210 of acid value in 50% solid matter
concentration.
[Production of Solvent Solution (p-3) of Resin (p)]
The solvent solution (p-3) of resin (p) was obtained in the same
manner as Example 61, except that the resin solution containing
styrene-acryl copolymer in 50% solid matter concentration 28 part
was used in place of the polyester (62) 14 part, the ethyl acetate
solution of isocyanate-containing prepolymer (.alpha.-1) 52 part
was used in place of the ethyl acetate solution of polyurethane
resin (61) 52 part, and the curing agent (.beta.-1) produced in
Production Example 65 5.3 part was used.
[Production of Resin Particles]
Resin particles (63) and a coating composition (63) were obtained
in the same manner as Example 61, except that the water-based
dispersion containing the resin fine particles (Q-2) was used in
place of the water-based dispersion containing the resin fine
particles (Q-1) and solvent solution (p-3) was used in place of the
solvent solution (p-1) of resin (p). The resin particles (63) had
Tg of 81.degree. C., 142 .mu.m of particle diameter, and 0.0057 of
volume average particle diameter ratio to the resin fine particles
(Q-1).
Example 64
[Synthesis of Polyester (63)]
The linear polyester (Aa-4) of Example 4 was synthesized and
employed as polyester (63).
[Production of Solvent Solution of Resin (p-4)]
Polyester (63) 70 part, the ethyl acetate solution containing
isocyanate-containing prepolymer (.alpha.-1) 30 part, the curing
agent (.beta.-2) produced in Production Example 66 1.8 part,
[Colorant dispersion] produced in Production Example 67 25 part,
[Release agent dispersion] produced in Production Example 68 50
part, and ethyl acetate 25 part were mixed and stirred evenly to
obtain a solvent solution (p-4) of resin (p).
[Production of Resin Particles]
Resin particles (64) were obtained in the same manner as Example
61, except that the water-based dispersion containing the resin
fine particles (Q-3) was used in place of the water-based
dispersion containing the resin fine particles (Q-1) and solvent
solution (p-4) was used in place of the solvent solution (p-1) of
resin (p). The resin particles (64) had Tg of 48.degree. C., 4.8
.mu.m of particle diameter, and 0.010 of volume average particle
diameter ratio to the resin fine particles (Q-3).
Further, the resin particles (64) 100 part were mixed with
colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co.,
Ltd.) 0.5 part by a sample mill to obtain a toner composition
(64).
Example 65
[Synthesis of Polyester (64)]
In a reaction container equipped with a cooling tube, a stirrer,
and a nitrogen introduction tube, polycondensation reaction of
bisphenol A-2 mole ethylene oxide adduct 570 part and terephthalic
acid 217 part was carried out at 230.degree. C. and a normal
pressure for 6 hours and a reduced pressure for 6 hours to obtain
polyester having 2,600 of Mn, 48 of hydroxy value and 2 of acid
value and then ring opening addition reaction of trimellitic acid
anhydride 26 part with the polyester was carried out at 180.degree.
C. and a normal pressure for 2 hours to obtain carboxyl-terminated
polyester (64) having 2,700 of Mn, 35 of hydroxy value, and 26 of
acid value. The polyester (64) had Tg of 48.degree. C.
[Production of Solvent Solution of Resin (p-5)]
The solvent solution (p-5) of resin (p) was obtained in the same
manner as Example 64, except that the polyester (64) was used in
place of the polyester (63).
[Production of Resin Particles]
Resin particles (65) and a coating composition (65) were obtained
in the same manner as Example 64, except that the water-based
dispersion containing the resin fine particles (Q-4) was used in
place of the water-based dispersion containing the resin fine
particles (Q-1) and solvent solution (p-5) was used in place of the
solvent solution (p-4) of resin (p). The resin particles (65) had
Tg of 48.degree. C., 5.2 .mu.m of particle diameter, and 0.01 of
volume average particle diameter ratio to the resin fine particles
(Q-4).
Example 66
[Production of Solvent Solution of Resin (p-6)]
The solvent solution (p-6) of resin (p) was obtained in the same
manner as Example 64, except that the ethyl acetate solution of
isocyanate-containing prepolymer (.alpha.-1) 30 part and the ethyl
acetate solution of polyurethane resin (1) produced in Example 61
was used in place of the curing agent (.beta.-2) produced in
Production Example 66.
[Production of Resin Particles]
Resin particles (66) and a toner composition (66) were obtained in
the same manner as Example 64, except that the water-based
dispersion containing the resin fine particles (Q-4) was used in
place of the water-based dispersion containing the resin fine
particles (Q-1) and solvent solution (p-6) was used in place of the
solvent solution (p-4) of resin (p). The resin particles (66) had
Tg of 53.degree. C., 5.0 .mu.m of particle diameter, and 0.010 of
volume average particle diameter ratio to the resin fine particles
(Q-4).
Comparative Example 61
[Synthesis of Polyester (65)]
The linear polyester (Aa'-5) of Comparative Example 1 was
synthesized and employed as comparative linear polyester (65).
[Synthesis of Polyester (66)]
The non-linear polyester (Ab'-5) of Comparative Example 1 was
synthesized and employed as comparative linear polyester (66).
[Production of Solvent Solution of Resin]
The solvent solution (X-1) of comparative resin was obtained in the
same manner as Example 61, except that polyester (65) was used in
place of the polyester (62) and polyester (66) 26 part and ethyl
acetate 26 part were used in place of the ethyl acetate solution of
polyurethane resin (1) 52 part.
[Production of Resin Particles]
Resin particles (X1) and a coating composition (X1) were obtained
in the same manner as Example 61, except that the solvent solution
of the comparative resin (X-1) was used in place of the solvent
solution (p-1) of the resin (p). The resin particles (X1) had Tg of
61.degree. C., 88 .mu.m of particle diameter, and 0.009 of volume
average particle diameter ratio to the resin fine particles
(Q-1).
Comparative Example 62
[Synthesis of Polyester (67)]
The linear polyester (Aa'-6) of Comparative Example 2 was
synthesized and employed as comparative linear polyester (67).
[Production of Oil Type Mixed Solution]
The solvent solution (X-2) of comparative resin was obtained in the
same manner as Example 64, except that polyester (67) was used in
place of the polyester (63) of Example 64 and polyester (66) 15
part and ethyl acetate 15 part were used in place of the ethyl
acetate solution of isocyanate-containing prepolymer (.alpha.-1) 30
part and the curing agent (.beta.-2) produced in Production Example
661.8 part.
[Production of Resin Particles]
Resin particles (X2) and a toner composition (X2) were obtained in
the same manner as Example 64, except that the solvent solution of
the comparative resin (X-2) was used in place of the solvent
solution (p-4) of the resin (p). The resin particles (X2) had Tg of
47.degree. C., 5.5 .mu.m of particle diameter, and 0.011 of volume
average particle diameter ratio to the resin fine particles
(Q-3).
Comparative Example 63
[Synthesis of Polyester (P67)]
The linear polyester (Aa'-7) of Comparative Example 3 was
synthesized and employed as comparative linear polyester (P67).
Since the polyester (P67) was not turned to be resin, it was not
used for resin particle production.
Comparative Example 64
[Synthesis of Polyester (68)]
The linear polyester (Aa'-8) of Comparative Example 4 was
synthesized and employed as comparative polyester (68).
[Synthesis of Polyester (69)]
The non-linear polyester (Ab'-8) of Comparative Example 4 was
synthesized and employed as comparative polyester (69).
[Production of Oil Type Mixed Solution]
The solvent solution (X-3) of comparative resin was obtained in the
same manner as Example 64, except that linear polyester (68) was
used in place of the polyester (63) of Example 64 and polyester
(69) was used in place of the ethyl acetate solution of
isocyanate-containing prepolymer (.alpha.-1) 30 part and the curing
agent (.beta.-2) produced in Production Example 661.8 part.
[Production of Resin Particles]
Resin particles (X3) and a toner composition (X3) were obtained in
the same manner as Example 64, except that the solvent solution of
the comparative resin (X-3) was used in place of the solvent
solution (p-4) of the resin (p). The resin particles (X3) had Tg of
51.degree. C., 5.3 .mu.m of particle diameter, and 0.009 of volume
average particle diameter ratio to the resin fine particles
(Q-3).
Evaluations were carried out by the following evaluation methods
and the evaluation results are shown in Table 7.
[Evaluation Methods]
[1] Volume average particle diameter
The volume average particle diameter of resin particles (61) to
(63) and comparative resin particles (X1) obtained in Example 61 to
63 and Comparative Example 61 was measured by dispersing the
particles and using Coulter Counter (Multisizer III manufactured by
US Coulter Electronics Corp.). [2] Leveling property
Each of the coating compositions (61) to (63) and comparative
coating composition (X1) obtained in Example 61 to 63 and
Comparative Example 61 was applied in a coating thickness of 40 to
60 .mu.m to a standardized plate of a zinc phosphate-treated steel
plate manufactured by Nippon Test Panel Co., Ltd. by electrostatic
coating using a commercialized corona charging spray gun and baked
at 180.degree. C. for 20 minutes and the surface smoothness was
observed by eye observation and evaluated according to the
following criteria: .circleincircle.: smooth and glossy surface,
.largecircle.: surface having slight roughness and gloss, .DELTA.:
rough surface and no gloss, and x: rough surface and trace of foams
existing and no gloss. [3] Thermal storability
Each of the coating compositions was stored at 40.degree. C. for 7
days and occurrence of melt adhesion was observed. The observation
was carried out by sieving each stored coating composition 50 g was
sieved by a standard sieve with 150 .mu.m mesh by shaking for 15
minutes and the amount of resin particles remaining on the sieve
was measured and the storability was evaluated based on the ratio
of the amount according to the following criteria:
.circleincircle.: less than 0.2% of agglomerates, .largecircle.:
less than 1% of agglomerates, .DELTA.: less than 2.0% of
agglomerates, and x: 2.0% or more of agglomerates. [4] Adhesion
property (Cohesion)
Each of the coating compositions was applied in a coating thickness
of 40 to 60 .mu.m to a standardized plate of a zinc
phosphate-treated steel plate manufactured by Nippon Test Panel
Co., Ltd. by electrostatic coating using a commercialized corona
charging spray gun and baked at 180.degree. C. for 20 minutes and
then the each coating was subjected to a shearing adhesion test
according to a method standardized in JIS K6830. The adhesion
property (Cohesion) was evaluated according to the following
criteria: .largecircle.: Complete cohesive failure, .DELTA.:
partial interfacial failure leaving traces of breakage, and x:
complete interfacial failure. [5] Water-proof adhesion
Each of the coating compositions of Examples and Comparative
Example was applied and baked in the above-mentioned manner and
then each coating was immersed in hot water at 40.degree. C. for 10
days. The longitudinal shear strength test was carried out
according to a method standardized in JIS K6830. Evaluation
criteria were same as those for the above-mentioned adhesion
property (Cohesion).
TABLE-US-00008 TABLE 7 Volume average Resin Surface Adhesion Water-
particle particle smooth- Thermal property proof diameter No. ness
storability (Cohesion) adhesion (.mu.m) Resin .circleincircle.
.circleincircle. .largecircle. .largecircle. 95 particle (61) Resin
.largecircle. .circleincircle. .largecircle. .DELTA. 120 particle
(62) Resin .circleincircle. .largecircle. .largecircle. .DELTA. 142
particle (63) Comparative X .DELTA. .DELTA. X 88 resin particle
(X1)
Evaluations were carried out by the following evaluation methods
and the evaluation results are shown in Table 8. [6] Minimum fixing
temperature (MFT)
According to the above-mentioned method. [7] Hot offset generationg
temperature (HOT)
According to the above-mentioned method. [8] Toner fluidity
According to the above-mentioned method. [9] Volume average
particle diameter
According to the above-mentioned method [1].
TABLE-US-00009 TABLE 8 Volume average MFT HOT Toner particle
diameter Resin particle No. (.degree. C.) (.degree. C.) fluidity
(.mu.m) Resin particle (64) 125 240 .largecircle..DELTA. 5.1 Resin
particle (65) 125 240 .largecircle. 5.0 Resin particle (66) 125 240
.largecircle. 5.3 Comparative resin 135 230 .DELTA.X 5.5 particle
(X2) Comparative resin 140 240 .largecircle..DELTA. 5.8 particle
(X3)
INDUSTRIAL APPLICABILITY
A toner composition of the invention containing a polyester resin
for a toner of the invention is excellent in the balance among the
low temperature fixing property, hot offset resistance, and
grindability and is useful for a toner for electrostatic image
development and particularly for a color toner.
The toner of the sixth invention is excellent in the balance among
the low temperature fixing property, hot offset resistance, and
grindability and is useful for a toner for electrostatic image
development and particularly for a color toner in terms of the
luster and transparency.
The composite resin particles of the seventh and eighth inventions
are highly useful for a powder coating, a resin for slush molding,
a toner to be used for electrophotography, electrostatic recording,
and electrostatic printing, a hot-melt adhesive, and other molding
materials.
* * * * *